阅读说明：本技术 金属和金属离子电池的纳米多孔导电骨架基体中的氟化物 (Fluorides in nanoporous conductive scaffolding matrices for metal and metal-ion batteries ) 是由 葛莱普·N·禹沈 伯格丹·兹迪亚科 亚历山大·T·雅各布斯 尤金·M·布迪切夫斯基 于 2014-11-26 设计创作，主要内容包括：本发明提供了一种包含复合材料颗粒的电池电极成分。每个复合材料颗粒都可包含例如活性氟化物材料以及所述活性氟化物材料设置在其内的纳米多孔导电骨架基体。活性氟化物材料用于在电池运行期间存储和释放离子。离子的存储和释放可导致活性材料的体积的实质性变化。所述骨架基体结构性地支撑活性材料、电气地互连活性材料并且适应活性材料的体积变化。(The present invention provides a battery electrode composition comprising composite particles. Each composite particle may comprise, for example, an active fluoride material and a nanoporous, electrically conductive scaffolding matrix within which the active fluoride material is disposed. Active fluoride materials are used to store and release ions during cell operation. The storage and release of ions can result in a substantial change in the volume of the active material. The scaffolding matrix structurally supports the active material, electrically interconnects the active material, and accommodates volume changes of the active material.)

1. A battery electrode composition comprising composite particles, each composite particle comprising:

an active fluoride material for storing and releasing ions during operation of the battery, wherein the storage and release of ions results in a substantial change in volume of the active material; and

a nanoporous, electrically conductive scaffolding matrix within which the active fluoride material is disposed, wherein the scaffolding matrix structurally supports the active material, electrically interconnects the active material, and accommodates volume changes of the active material.

2. The battery electrode composition of claim 1, wherein the scaffolding matrix comprises pores having an average characteristic pore width in a range of about 1 nanometer to about 10 nanometers.

3. The battery electrode composition of claim 1, wherein the active fluoride material comprises a first metal fluoride and a second metal fluoride.

4. The battery electrode composition of claim 1, wherein each composite particle further comprises a shell at least partially encasing the active fluoride material and the scaffolding matrix, the shell being substantially permeable to ions stored and released by the active fluoride material.

5. The battery electrode composition of claim 4, wherein the shell comprises a protective layer formed of a material that is substantially impermeable to electrolyte solvent molecules.

6. The battery electrode composition of claim 4, wherein the shell comprises an active material layer, and wherein the active material layer is formed from an active material different from an active fluoride material disposed within the scaffolding matrix.

7. The battery electrode composition of claim 6, wherein the active material of the active material layer has a substantially lower capacity relative to the active fluoride material.

8. The battery electrode composition of claim 4, wherein the shell comprises a porous layer having a smaller average pore size than the scaffolding matrix.

9. The battery electrode composition of claim 8, wherein pores in the porous layer of the shell are infiltrated with an active fluoride material that is the same as an active fluoride material disposed within the scaffolding matrix.

10. The battery electrode composition of claim 4, wherein the shell is a composite material comprising an inner layer and an outer layer.

11. The battery electrode composition of claim 10, wherein the inner layer is a porous layer having a smaller average pore size than the scaffolding matrix, and wherein the outer layer is: a protective layer formed of a material that is substantially impermeable to electrolyte solvent molecules, or (ii) an active material layer formed of an active material that is different from the active material disposed within the scaffolding matrix.

12. The battery electrode composition of claim 4, wherein the shell is a composite material comprising two or more materials disposed in an interpenetrating configuration such that each material in the composite material contacts the scaffolding matrix.

13. The battery electrode composition of claim 1, each composite particle further comprising an outer channel pore extending from an outer surface of the scaffolding matrix towards a center of the scaffolding matrix, thereby providing a channel for ion diffusion into an active material disposed within the scaffolding matrix, wherein at least some of the outer channel pores are filled with: a porous material having a microstructure different from the skeletal matrix, (ii) an active material different from an active fluoride disposed within the skeletal matrix, and/or (iii) a solid electrolyte material.

14. The battery electrode composition of claim 1, each composite particle further comprising a protective material at least partially impregnated into the scaffolding matrix in a radially variable composition along a radius of the particle, the protective material being substantially permeable to ions stored and released by the active fluoride material.

15. A method of making a battery electrode composition comprising composite particles, the method comprising:

providing an active fluoride material that stores and releases ions during operation of the battery, wherein the storage and release of ions results in a substantial change in volume of the active material; and

forming a nanoporous, electrically conductive scaffolding matrix within which the active fluoride material is disposed, wherein the scaffolding matrix structurally supports the active material, electrically interconnects the active material, and accommodates volume changes of the active material.

16. The method of claim 15, wherein forming the scaffolding matrix comprises:

forming a carbon-containing precursor;

oxidizing and carbonizing the carbon-containing precursor to form carbonized particles; and

activating the carbonized particles at an elevated temperature to form a skeletal matrix having a pore volume greater than 50% by volume.

17. The method of claim 15, wherein the scaffolding matrix infused with the active fluoride material is formed into a powder comprising particles, the method further comprising:

mixing the activated fluoride material infused scaffolding matrix particles with a binder;

the adhesive-bonded particles are cast onto a metal foil current collector.

18. The method of claim 15, further comprising forming a shell at least partially encasing the active fluoride material and the scaffolding matrix, the shell being substantially permeable to ions stored and released by the active material.

19. The method of claim 18, wherein at least a portion of the shell material is deposited by chemical vapor deposition.

20. The method of claim 18, wherein at least the exterior of the shell is electrochemically deposited during one or more initial cell cycles, during which electrochemical deposition at least some electrolyte components are electrochemically decomposed.

Technical Field

The present application relates generally to energy storage devices and more particularly to aspects of metal and metal-ion battery technology.

Background

Due in part to their relatively high energy density, light weight, and potentially long life, many consumer electronics desire the use of advanced metal-ion batteries, such as lithium-ion (Li-ion) batteries. However, while they are becoming increasingly popular commercially, these batteries need further development, especially for potential applications in low or zero emission applications, hybrid electric or all-electric vehicles, consumer electronics, energy efficient cargo and cargo ships, aerospace applications, and electrical grids.

Conversion electrodes for lithium ion batteries, such as fluorides, sulfides, oxides, nitrides, phosphides, hydrides, and others, provide high gravimetric and volumetric capacities.

In particular, fluorides provide a combination of relatively high average voltage and high capacity, but suffer from several limitations for various metal ion (e.g., lithium ion) battery chemistries. For example, it is said that only selected metal fluoride particles provide some suitable cycling stability in lithium ion battery cells (specifically, AgF)₂、FeF₂、FeF₃、CoF₂And NiF₂). It is generally believed that many other metal fluorides cannot be practically used in lithium ion batteries because irreversible changes can occur in the cathode during battery operation. For example, in the insertion of lithium ions into certain other fluorides (e.g., CuF)₂) Elements that initially form fluoride (e.g., in CuF) during and when LiF is subsequently formed during the conversion reaction₂In the case of Cu) produces electrically insulating (Cu) nanoparticles. Because of electrical insulation, such nanoparticles cannot electrochemically react with LiF to convert back to CuF during subsequent Li extraction₂Thereby preventing reversibility of the conversion reaction. Therefore, after discharge, the battery cell cannot be charged back to the initial capacity.

However, even those metal fluorides (e.g., FeF) considered most practical due to their relatively reversible operation and relatively low cost₂、FeF₃、CoF₂And NiF₂) Also subject to various limitations, including: low conductivity, which limits their use and the energy and power characteristics of the cell; (ii) low ionic conductivity, which limits their use and the energy and power characteristics of the battery; and (iii) volume changes during metal ion insertion/extraction, which can lead to mechanical and electrical degradation of the electrode during cell operation. Thus, while fluoride-based cathodes have theoretical advantages, their practical application in metal ion batteries, for example, is difficult to achieve. The cell produced with fluoride-based cathode has the disadvantages of poor stability, volume change, slow charging and high impedance.

Several approaches have been developed to overcome some of the above difficulties, but none have been entirely successful in overcoming all of them.

For example, reducing the particle size allows the ion diffusion distance to be reduced as well, and provides a solution to the limitation of low ionic conductivity. However, nanopowders suffer from high electrical resistance due to the multiple high resistance contact points formed between the individual particles. In addition, the small particle size increases the specific surface area for undesirable electrochemical side reactions. Furthermore, merely reducing particle size does not address and in some cases may exacerbate other limitations of these materials, such as volume changes and weakening of the particle-binder interface. Finally, it is technically difficult to manipulate nanoparticles and use them to make dense electrodes, as compared to micron-sized particles used in cathode formulations. The nanoparticles are difficult to uniformly disperse within the conductive carbon additive and binder of the cathode and are prone to undesirable nanoparticle agglomerate formation. The formation of such agglomerates reduces the electrode density (and thus the volume standard capacity and energy density of the battery cell), reduces the electrode stability (because the binder and conductive additives do not connect individual particles within such agglomerates), and reduces the capacity usage (because some of the nanoparticles become electrically insulating and therefore do not participate in lithium ion storage).

In another approach, selected metal fluoride particles (specifically, FeF) that provide some suitable cycling stability in lithium ion battery cells₂、FeF₃、CoF₂And NiF₂) May be mechanically mixed with (as described, for example, in U.S. patent No.7,625,671B2, in some cases by using high energy milling) or deposited onto the surface of a conductive matrix, such as carbon black, graphite, multi-walled carbon nanotubes, or carbon fibers. In this case, the high conductivity of carbon improves the conductivity of the electrode. However, phase inversion and the above-mentioned volume change during the operation of the battery may induce the separation of the active material from the conductive additive, thereby causing an increase in resistance and deterioration of the battery.

In yet another method, selected metal fluoride particles (specifically, FeF)₂Particles) may be coated with a solid multi-walled graphitic carbon shell. In this case, the conductivity of the metal fluoride cathode can be improved. However, the above-mentioned volume changes during metal ion insertion can destroy the graphitic carbon coating and induce irreversible capacity loss. Similarly, subsequent charge and discharge cyclesThe phase inversion during this time can initiate separation of the active material from the graphite carbon shell, resulting in increased electrical resistance and degradation of the battery.

Accordingly, there remains a need for improved metal and metal-ion batteries, components, and other related materials and methods of manufacture.

Disclosure of Invention

Embodiments disclosed herein address the above stated needs by providing improved battery components, improved batteries made thereby, and methods of making and using the improved battery components.

The present invention provides a battery electrode composition comprising composite particles. Each composite particle may comprise, for example, an active fluoride material and a nanoporous, electrically conductive scaffolding matrix within which the active fluoride material is disposed. Active fluoride materials are used to store and release ions during cell operation. The storage and release of ions can result in a substantial change in the volume of the active material. The scaffolding matrix structurally supports the active material, electrically interconnects the active material, and accommodates volume changes of the active material.

The scaffolding matrix may comprise pores having an average characteristic pore width, for example, in a range of about 1 nanometer to about 10 nanometers. In certain designs, the active fluoride material may comprise a first metal fluoride and a second metal fluoride.

In certain designs, each composite particle may further comprise a shell at least partially encasing the active fluoride material and the scaffolding matrix, the shell being substantially permeable to ions stored and released by the active fluoride material. For example, the shell may comprise a protective layer formed of a material that is substantially impermeable to electrolyte solvent molecules. As another example, the shell may contain a layer of active material, wherein the layer of active material is formed from an active material different from the active fluoride material disposed within the scaffolding matrix. The active material of the active material layer may have a substantially lower capacity relative to the active fluoride material. As another example, the shell may comprise a porous layer having a smaller average pore size than the scaffolding matrix. The pores in the porous layer of the shell are permeable to the same active fluoride material as that disposed within the scaffolding matrix. As another example, the shell may be a composite material comprising an inner layer and an outer layer. The inner layer may be a porous layer, e.g., having a smaller average pore size than the scaffolding matrix, and the outer layer may be, e.g., (i) a protective layer formed of a material that is substantially impermeable to electrolyte solvent molecules, or (ii) an active material layer formed of an active material that is different from the active material disposed within the scaffolding matrix. As another example, the shell may be a composite material comprising two or more materials arranged in an interpenetrating configuration such that each material in the composite material contacts the scaffolding matrix.

In certain designs, each composite particle may further comprise an outer channel pore extending from the outer surface of the scaffolding matrix towards the center of the scaffolding matrix, thereby providing a channel for diffusion of ions into the active material disposed within the scaffolding matrix. At least some of the outer channel pores may be filled with: a porous material having a microstructure different from the scaffolding matrix, (ii) an active material different from an active fluoride material disposed within the scaffolding matrix, and/or (iii) a solid electrolyte material.

In certain designs, each composite particle may further comprise a protective material at least partially impregnated into the scaffolding matrix with a radially variable composition along a radius of the particle, the protective material being substantially permeable to ions stored and released by the reactive fluoride material.

The invention also provides methods of making battery electrode compositions comprising the composite particles. Example methods may include, for example, providing an active fluoride material to store and release ions during operation of the cell, and forming a nanoporous, electrically conductive scaffolding matrix within which the active fluoride material is disposed. The storage and release of ions can result in a substantial change in the volume of the active material. The scaffolding matrix may structurally support the active material, electrically interconnect the active material, and accommodate volume changes of the active material.

In certain designs, forming the skeletal matrix may include, for example, forming a carbon-containing precursor, oxidizing and carbonizing the carbon-containing precursor to form carbonized particles, and activating the carbonized particles at an elevated temperature to form the skeletal matrix having a pore volume greater than 50% by volume. In certain designs, the active fluoride material infused scaffolding matrix may be formed, for example, as a powder (which includes particles), by a method further comprising mixing the active fluoride material infused scaffolding matrix particles with a binder and casting the binder-bound particles onto a metal foil current collector. In certain designs, the method may further comprise forming a shell at least partially encasing the active fluoride material and the scaffolding matrix, the shell being substantially permeable to ions stored and released by the active material. In some designs, at least a portion of the shell material may be deposited by chemical vapor deposition. In certain designs, at least the exterior of the shell may be electrochemically deposited during one or more initial cell cycles during which electrochemical decomposition of at least some electrolyte components occurs.

Drawings

The accompanying drawings are included to aid in the description of embodiments of the invention and are provided solely for illustration and not limitation of the embodiments.

Fig. 1 illustrates an example battery (e.g., lithium ion) in which the compositions, materials, methods, and other techniques described herein, or combinations thereof, may be applied in accordance with various embodiments.

Fig. 2 shows a comparison of the voltage distribution of lithium intercalated into iron fluoride and lithium intercalated into copper fluoride.

Fig. 3A-3B show two specific examples of active fluoride nanoparticles or active fluoride nanoplates infiltrated into a conductive scaffolding matrix of a nanoporous material having (a) straight pores and (B) curved pores.

Fig. 4A-4D show four specific examples of the relative change in the average pore volume of the scaffolding matrix as a function of distance from the center of the particle toward the surface of the particle.

Fig. 5 shows a schematic diagram of an exemplary charge and discharge process within the pores in which lithium ions react with metal fluoride nanoclusters to form nanoclusters of fluoride forming elements and nanoclusters of LiF.

Fig. 6A-6B show two specific examples of fluoride-containing composites, in which active fluoride nanoparticles or active fluoride nanoplatelets are infiltrated into a scaffolding matrix of a nanoporous material, and in which the overall fluoride matrix composite particles are further coated with a protective layer of electrolyte solvent impermeable shell material capable of conducting lithium ions.

Fig. 7A-7B illustrate two specific examples of fluoride-containing composites having a protective shell layer that is a composite material, in accordance with various embodiments.

Fig. 8A-8B illustrate two specific examples of fluoride-containing composites according to various embodiments, in which the fluoride conductive core contains relatively small (e.g., less than 6nm) pores to confine fluoride and relatively large "channel" pores (e.g., greater than about 6nm) designed to provide rapid transport of ions from the electrolyte solution into the core of the particle.

Fig. 9A-9D show four specific examples of metal fluoride-containing composites in various embodiments, wherein the composites additionally comprise embedded active materials or surface protection materials, wherein the relative mass fractions of these materials form a gradient from the core to the surface of the particle, and wherein a higher concentration of the protection (or embedded active) material is close to the surface of the particle.

Fig. 10A-10B show two specific examples of single fluoride nanoparticles confined within the pores of a conductive scaffolding matrix and further coated with another metal fluoride (which may provide advantageous stability or improved rate performance over a potential operating range) or another material-e.g., a protective layer of an embedded active material, a solid electrolyte, or a mixed conductor.

11A-11B show two specific examples of the relative change in average mass fraction of fluoride as a function of distance from the center to the surface of the fluoride-containing composite particle.

12A-12D show four specific examples of the relative change in the average mass fraction of the protective material as a function of distance from the center to the surface of the fluoride-containing composite particle.

Fig. 13A-13D show four specific examples of the relative change in the average mass fraction of the embedded active material as a function of distance from the center to the surface of the fluoride-containing composite particle.

Fig. 14A-14C show three specific examples of the relative change in the average mass ratio of two metal fluorides (MF1 and MF2) as a function of distance from the center to the surface of the composite particle, where one of the metal fluorides (e.g., MF1) provides a higher energy density and the other (e.g., MF2) improves the stability or rate performance of the composite.

Fig. 15 shows an example of a building block for a lithium-ion battery in which electrodes of varying volume and thickness (e.g., each having a variation in volume ratio of more than 6%) are designed to counteract the variation in cell size during operation of the battery.

Fig. 16 shows a specific example of an electrode composed of fluoride infiltrated into the conductive skeletal matrix of a nanoporous material, wherein the electrode is further coated with a solid electrolyte or the solid electrolyte fully infiltrates the pores between the individual fluoride-containing composite particles.

Fig. 17 shows a specific example of irregularly shaped active particles comprising fluoride impregnated in a conductive nanoporous scaffolding matrix.

Fig. 18A-18D show four specific examples using skeletal particles with macropores.

Fig. 19 includes a flow chart illustrating an example method of making a metal fluoride-containing composite electrode.

20A-20B include a flow chart illustrating another exemplary method of making a metal fluoride-containing composite electrode.

21A-21B include a flow chart illustrating another exemplary method of making a metal fluoride-containing composite electrode.

22A-22B include a flow diagram illustrating another example method of making a metal fluoride containing composite electrode with a protective coating formed in situ after battery assembly.

Detailed Description

Various aspects of the invention are disclosed in the following description and drawings directed to specific embodiments of the invention. The term "embodiments of the invention" does not require that all embodiments of the invention include the discussed feature, advantage, process or mode of operation and that alternative embodiments may be devised without departing from the scope of the invention. Additionally, well-known elements of the invention may not have been described in detail or may be omitted so as not to obscure the other elements, the more relevant details.

While the following detailed description may describe certain examples in the context of lithium (Li) and lithium ion (Li-ion) batteries (for the sake of brevity and convenience, and because Li technology is currently prevalent), it should be understood that aspects of the present invention may be applied to other rechargeable and primary batteries, metal batteries, and metal-ion batteries (e.g., Na-ion batteries, Mg-ion batteries, and other batteries). Further, while the following description may also describe certain examples of material formulations in a lithium-free (e.g., charged) state, it should be understood that aspects of the present invention may be applied to lithium-containing electrodes (e.g., in a partially or fully charged state).

Fig. 1 illustrates an example metal-ion (e.g., lithium-ion) battery to which the components, materials, methods, and other techniques described herein, or a combination thereof, may be applied in accordance with various embodiments. A cylindrical battery is shown here for exemplary purposes, but other types of arrangements may also be used as desired-including prismatic or pouch (laminate-type) batteries. The example battery 100 includes a negative anode 102, a positive cathode 103, a separator 104 disposed between the anode 102 and the cathode 103, an electrolyte (not shown) impregnating the separator 104, a battery housing 105, and a sealing member 106 sealing the battery housing 105.

Both conventional liquid and solid electrolytes may be used in the designs herein. Conventional electrolytes for Li or Na-based batteries of this type generally comprise a mono-lithium or sodium salt in a mixture of solvents (e.g., a mixture of carbonates) (e.g., LiPF for a lithium ion battery)₆And NaPF for Na ion batteries₆Or NaClO₄). The most common salt used in lithium ion battery electrolytes is, for example, LiPF₆However, less common salts include lithium tetrafluoroborate (LiBF)₄) Lithium perchlorate (LiClO)₄) Lithium bis (oxalato) borate (LiB (C)₂O₄)₂) Lithium difluorooxalato borate (LiBF)₂(C₂O₄) Lithium imides (e.g., SO)₂FN^-(Li⁺)SO₂F、CF₃SO₂N^-(Li⁺)SO₂CF₃、CF₃CF₂SO₂N^-(Li⁺)SO₂CF₃、CF₃CF₂SO₂N^-(Li⁺)SO₂CF₂CF₃、CF₃SO₂N^-(Li⁺)SO₂CF₂OCF₃、CF₃OCF₂SO₂N^-(Li⁺)SO₂CF₂OCF₃、C₆F₅SO₂N^-(Li⁺)SO₂CF₃、C₆F₅SO₂N^-(Li⁺)SO₂C₆F₅Or CF₃SO₂N^-(Li⁺)SO₂PhCF₃And other substances), among others. Electrolytes for Mg ion, Ca ion and Al ion batteries are generally rare because these batteries are in an early stage of development. They may contain different salts and solvents (in some cases, ionic liquids may replace organic solvents for some applications).

Alternatively, the solid electrolyte may be a fluoride-based cathode electrolyteProviding certain advantages such as antioxidant stability at high cathodic potentials, reducing undesirable side reactions between the cathode and the electrolyte, and improving safety. Examples of solid ceramic electrolytes include sulfur-based electrolytes (e.g., Li)₂S-P₂S₅、Li₂S-Ga₂S₃-GeS₂、Li₂S-SiS₂Etc.), an oxide-based electrolyte (e.g., Li-La-Ti-O garnet, Li-La-Ta-O garnet, Li-Si-O glass, Li-Ge-O glass, Li₉SiAlO₈Etc.), mixed sulfur oxide electrolytes (e.g., Li)₂S-SiS₂-Li₄SiO₄、LiI-La₂O₂S-La₂O₂S₂Etc.) and many others. The inability of ceramics to accommodate volume changes that occur during charge and discharge cycles has prevented the use of solid electrolytes for conversion-based cathodes. They are difficult to use in fluoride-based cathodes because of the large volume change of the fluoride-based active cathode particles.

Conventional cathode materials employed in metal-ion batteries are of the intercalation type. During discharge of the battery, metal ions intercalate and occupy interstitial sites of this material. However, such cathodes have a small gravitational capacity and more importantly a small volumetric capacity: typically less than 220mAh/g active material and less than 600mAh/cm at the electrode potential³. This low capacity of the intercalation-type cathode limits the energy density and specific energy of the metal-ion battery.

Fluoride-based cathodes are due to their very high capacity-in some cases exceeding 300mAh/g (more than 1200mAh/cm at the electrode potential)³) But may have significant technical potential. For example, FeF₃Providing a theoretical specific capacity of 712 mAh/g; FeF₂Providing a theoretical specific capacity of 571 mAh/g; MnF₃Providing a theoretical specific capacity of 719 mAh/g; CuF₂Providing a theoretical specific capacity of 528 mAh/g; NiF₂Providing a theoretical specific capacity of 554 mAh/g; PbF₂Providing a theoretical specific capacity of 219 mAh/g; BiF₃Providing a theoretical specific capacity of 302 mAh/g; BiF₅Providing a theoretical specific capacity of 441 mAh/g; SnF₂Providing a theoretical specific capacity of 342 mAh/g; sn (tin)F₄Providing 551mAh/g theoretical specific capacity; SbF₃Providing a theoretical specific capacity of 450 mAh/g; SbF₅Providing a theoretical specific capacity of 618 mAh/g; CdF₂Providing a theoretical specific capacity of 356 mAh/g; and ZnF₂Providing a theoretical specific capacity of 519 mAh/g.

In addition, fluoride-based cathodes also have the potential for low cost where the fluoride-forming elements are inexpensive. The 5-year average wholesale cost of many fluoride-forming elements is quite low. For example, in 2013, the cost of Fe was only about $ 0.2/kg; the cost of Cu is only about $4-9/kg, the cost of Zn is only about $ 1-2/kg; the cost of Cd is only about $1 kg; the cost of Pb is only about $1-2 kg; and Sb costs only about $6-15 kg.

However, many fluorides (e.g., CuF) with high theoretical capacity and high theoretical energy density are believed to be₂、NiF₂、PbF₂、BiF₃、BiF₅、SnF₂、SnF₄、SbF₃、CdF₂、ZnF₂And other fluorides) cannot be practically applied in rechargeable lithium ion batteries because of their lack of stability previously observed and the large polarization phenomena observed in experiments when they are used in conventional cathode constructions (where metal fluorides are mechanically mixed with carbon additives or deposited on the outer surface of carbon particles).

These so-called "impractical" fluorides (e.g., CuF)₂、PbF₂、SnF₂、CdF₂、ZnF₂And other fluorides) relative to the more commonly used FeF₃The advantage of this is a smoother discharge curve, which enables lithium ion batteries based on such cathodes to maintain a more constant voltage when using most of their theoretical capacity.

FIG. 2 is a graph showing CuF₂Discharge curve of cathode and exemplary FeF₂And FeF₃Comparison of the discharge curves of the base cathodes shows CuF₂With significantly smoother performance.

Fluoride has significant structural and volumetric changes with cycling of the cell, compared to the small structural, chemical and volumetric differences observed during lithium ion insertion/extraction of the cathode intercalation compound. A migration/conversion process occurs during Li insertion, wherein Li migrates the fluoride-forming solid elements (e.g., metals or semi-metals or in some cases semiconductors), resulting in the formation of solid LiF and clusters of fluoride-forming elements-typically only 2-10nm in size. The size of these clusters can be related to the mobility of the metal in the intermediate reaction product. Reversible Li insertion and extraction is feasible in cases where the diffusion distance between these thermodynamically stable structures is small and when electrons can be supplied to support the electrochemical reaction.

Theoretically, the Li capacity of a fluoride is determined by its stoichiometric ratio and the density of the metal forming the fluoride, according to the following reaction (which is assumed to be fully reversible):

wherein M is a fluoride-forming element.

Mechanistically, it has been found that Li initially intercalates into certain metal fluorides (e.g., FeF) as intercalation proceeds₂And FeF₃) In (1). For example, in Li and FeF₃During the electrochemical reaction of (a), Li is first inserted into the structure to form:

Li⁺+e^-+FeF₃→LiFeF₃(formula 2)

Only after additional Li insertion, the conversion reaction converts the reaction product into LiF and interconnected Fe nanoparticles according to the following formula:

2Li⁺+2e^-+LiFeF₃→ 3LiF + Fe (equation 3)

As discussed in the background above, conventional fluoride cathodes may be limited, for example, (i) low conductivity, (ii) low ionic conductivity, and (iii) volume change during metal ion insertion/extraction. Other limitations include (iv) gas generation during fluoride reaction with electrolyte (especially at high potentials) -which can lead to cell degradation, (v) surface species formation during surface reactions with electrolyte-which can increase resistance and decrease reversibility of electrochemical reactions, (vi) decomposition of metal fluorides during cycling-which can increase resistance, damage Solid Electrolyte Interphase (SEI) layers on the anode and decrease power performance and cycling stability of the cell, and (vii) irreversible changes occur within their structure during cell operation-which can also lead to irreversible capacity loss.

The present application provides advanced composite materials for battery electrodes formed of nanoporous materials (preferably having pores in the range of between about 0.5nm to about 10nm, but in some designs having pores up to 500nm or more), with an active fluoride material disposed in a generally conductive matrix. As discussed in more detail below, the present invention provides several advantages over conventional designs by confining the reactive fluoride material to this type of "framework" matrix. For example, confining the active fluoride material within such a matrix (as opposed to surface deposition) helps to avoid the generally undesirable agglomeration of individual active material particles. As described in more detail below, such a matrix may additionally help stabilize the particle size so that the expansion of the active material may be accommodated by the pores present in the metal fluoride-filled conductive matrix composite. The conductivity characteristics of the matrix may allow for reduced resistance and increased rate performance. The skeletal nature of the matrix may further allow for the formation of a protective shell around the composite particles that is mechanically and electrochemically stable during cycling and volumetric changes occurring within the metal-fluoride (MF) active material.

Fig. 3A-3B illustrate two example battery electrode compositions including fluoride impregnated into a conductive nanoporous scaffolding matrix, according to certain example embodiments. In each of the illustrated example designs, the composite particle is shown as having pores 302, conductive pore walls 304, and fluoride 306 infiltrated within the pores 302.

According to the reaction described above (equation 1), the "active" fluoride stores and releases metal ions (e.g., lithium ions in a lithium or lithium-ion battery) during operation of the battery. As discussed above, storing and releasing these metalsThe ions cause substantial changes in the volume of the active material, which in conventional designs can result in loss of electrical contact within the electrode and thus rapid loss of capacity during cell operation. Additionally, in some cases, clusters of fluoride-forming elements (e.g., in CuF)₂In the case of Cu) may form isolated particles that are not electrically connected to each other. Similarly, highly electrically isolated LiF can become electrically disconnected from the current collector. In this case, the conventional design of the electrodes or electrode particles does not allow the reversible storage and release of lithium ions during the operation of the battery, since such a process requires the uninterrupted transport of electrons into (or out of) the active material. Further, in some cases (e.g., in CuF)₂In the case of (a), rapid diffusion of fluoride-forming elements combined with high interfacial energy between, for example, LiF and fluoride-forming elements, results in physical separation of LiF from fluoride-forming elements during Li insertion. In conventional designs, this greatly limits the rate and reversibility of the reformation of initial fluorides during Li extraction due to mass transport limitations stemming from the partitioning discussed above.

However, in the designs shown in fig. 3A-3B herein, the volume change accompanying the conversion reaction (e.g., given by equation 1) can be accommodated by the pores of the nanoporous scaffold matrix. To maximize the volumetric capacity of the composite, the pore volume of the fluoride-filled scaffolding matrix may be beneficially optimized such that only a small amount of the volumetric pores (preferably, less than about 15%) are unoccupied by LiF and fluoride-forming materials after Li insertion with full discharge. The design shown here additionally greatly improves the rate and reversibility of battery operation. When the pore size of the scaffolding matrix becomes small, electrons can not only be transported through the matrix material during Li insertion but also generate channels from the pore walls to the electrochemical reaction sites and return during Li extraction. In order to achieve reasonably high reaction rates, it may be advantageous to limit the channel distance to about 3-5nm or less. Thus, the pores of the nanoporous scaffold matrix may preferably be less than 10nm wide.

For designs where the pores contain conductive nanoparticles (initially added or formed during the conversion reaction or more generally during cell operation), pores in the range of about 10nm to about 500nm may also be suitable. However, in some cases, these larger pores may result in reduced power performance characteristics. On the other hand, pores that are too small (e.g., pores less than about 0.5 nm) may make it more challenging to uniformly penetrate fluoride into their pore structure.

Finally, this design confines the initial fluoride as well as clusters of LiF and fluoride-forming elements to small nanopores. In this case, the skeletal matrix forces better contact between LiF and clusters of fluoride-forming elements, thereby greatly improving the rate of charging. Furthermore, if the scaffolding matrix has a certain elasticity and a relatively high elastic modulus (e.g., young's modulus greater than about 5MPa), elastic deformation of the matrix material during Li insertion will facilitate extraction of Li by lowering the reaction energy barrier achieved by releasing its stress energy through such extraction. This additionally improves the charging rate of the battery.

As one example, porous carbon (e.g., having sp in excess of 90%)²Binding atoms) may be used as the conductive skeletal matrix. Because the capacity of carbon is small in the cathode voltage range of interest (above 1.5V for Li/Li + in the case of lithium or lithium-ion batteries), it may be preferable to minimize its absolute mass and the volume occupied by its pore walls while maintaining the desired pore size and conductivity. It has been found that most pore walls work reasonably well for a monolayer thick porous carbon, providing a large pore volume and sufficiently high conductivity while minimizing the volume occupied by "inactive" carbon atoms. A "perfect" porous carbon particle having slot-shaped pores and pore walls consisting of a monolayer of graphite atoms may have a size of about 2630m²Specific surface area in g. Have been found to have a thickness of greater than 500m²G (more preferably higher than 1000 m)²Empirical measurements of Brunauer, Emmett and teller (bet) specific surface area porous carbons work well as conductive substrates for fluoride penetration. An example of a large surface area porous carbon is activated carbon. It can beTo be produced by pyrolysis of a carbon-containing organic precursor and subsequent chemical or physical activation thereof (partial oxidation of the carbon produced for the purpose of improving its pore volume and specific surface area). Further preferably, the porous carbon may have porosity occupying at least 50% (preferably, more than 70% and less than about 95% by volume) of the total volume. The smaller pore volume provides less room for fluoride penetration and may therefore reduce the volume capacity of the particles infiltrated with fluoride. Conversely, a pore volume higher than 95% reduces the mechanical properties provided by the particles (which can make the electrodes less stable) and additionally makes them more difficult to handle because of the very low density. Activated carbon particles produced in a conventional manner typically have a majority of pores in the 0.3nm to 10nm range. It has been found that those activated carbons having a majority of pores (preferably, more than 80% by volume) in the range of about 0.5nm to about 10nm are particularly useful as fluoride-infiltrated conductive scaffolding matrices.

In certain examples, the carbon backbone matrix may be doped with or function as other species (e.g., nitrogen) to increase lithium ion transport or to increase its wetting characteristics.

As further shown in fig. 3A-3B, the aperture may be straight as shown in fig. 3A or curved as shown in fig. 3B. Activated carbon typically has irregularly shaped, curved pores. The orientation of the pores may vary depending on the sample preparation. It may also vary within a single particle. For example, in the center of the particle, the pores may be in any direction or direction along their radius, while closer to the surface the pores may have a direction parallel to the surface of the particle. In this case, favorable mechanical characteristics can be achieved. Further, in some cases, the formation of a protective coating for stabilizing the metal fluoride from reversible changes and undesired reactions with the electrolyte (as discussed in more detail below) may be simplified.

Various methods can be used to synthesize and infiltrate fluoride into the conductive nanoporous scaffold matrix. Most fluorides can be synthesized by relatively simple reactions. A first group of such reactions involves oxides (e.g.,metal oxide) with hydrofluoric acid (HF) in the form of a gas or liquid (aqueous solution). The main feature of this process is that the metal does not change its oxidation state. Generally, such processes can be used to obtain metal fluorides (e.g., Sn) in their lower oxidation states²⁺Not Sn⁴⁺). Sometimes, in the case of hydrolyzed fluorides, HF can react directly with a metal (e.g., Zn) to form a metal fluoride (e.g., ZnF)₂) And (3) solution. This solution can penetrate into the pores of the matrix and dry to form fluorides that are confined within the matrix pores of the scaffold.

The second route to metal fluorides is to carry out a reaction between a metal or metal oxide and fluorine or a fluorinating agent. Examples of the latter include, but are not limited to, diethylamine trifluoride, tris (dimethylamino) thiodifluoro-trimethyl-silicon, and the fluorides of xenon. The oxidation state of the metal in the fluoride produced is generally the highest (2 Sb) because of the strong oxidizing properties of fluorine³⁺+5F₂→SbF₅). Another common approach to synthesizing water-insoluble fluorides within the pores of a conductive matrix is to perform an ion exchange reaction between a dissolved salt of a fluoride-forming element (e.g., a transition metal) and a water-soluble fluoride (typically an alkali metal fluoride). Because of the instability of transition metal fluorides, the latter precipitate during the reaction. The oxidation state of the transition metal does not change during the ion exchange reaction. The method has the advantage of eliminating F with high toxicity and corrosiveness in the process₂And HF. In addition, the size of the fluoride particles obtained can be adjusted over a wide range by varying the concentrations of the reactants, the order in which they are mixed, and the addition of the surfactant.

Yet another method for infiltrating fluoride into the framework pores involves the use of soluble fluoride precursors. Such a method may include the steps of: preparing a solution of a fluoride precursor, (ii) infiltrating the solution into the framework pores, (iii) subsequently evaporating the solvent (steps ii and iii may be repeated multiple times to achieve high fluoride loading), and (iv) thermally annealing to decompose the fluoride precursor into fluoride and removable volatile species. For example, fluorosilicates (e.g., FeSiF)₆·H₂O) may be infused into the framework pores, dried, and the resulting salt may be converted to a metal fluoride (e.g., ferric fluoride, FeF) by annealing (e.g., in an inert argon (Ar) gas)₂). The annealing process is to mix FeSiF₆·H₂Decomposition of O into FeF₂(more typically FeF)_x) Water vapor and volatile SiF₄(SiF₄Boiling point 86 deg.c) from which volatile compounds are removed. In some cases, initial annealing in an oxygen-containing gas may initiate the formation of FeF from the same precursor₃. The process of Metal Fluoride (MF) infiltration may be repeated multiple times in order to achieve a desired fraction of MF in the composite.

As described above, for soluble salts, the simplest method of infiltrating them into a porous matrix may involve the following steps: wetting the matrix with a salt solution in a solvent, and (ii) subsequently evaporating the solvent. This process may also be repeated one or more times to increase the loading of the framework with fluoride material. Solutions of different fluorides may be combined or alternatively applied to obtain mixed fluoride compositions within the framework. Solvent-insoluble fluorides can be prepared in a form in which small nanoparticles are suspended in a suitable liquid medium. Subsequently, the porous framework may be impregnated with the nanosuspension and the liquid evaporated. This process may be repeated in order to increase the loading of the metal fluoride. The size of such particles should be generally smaller than the size of the pores. In some cases, both the perfusion solution and the suspension may be performed in combination for the purpose of filling the matrix with a mixture of different compounds. This may be necessary to improve material capacity or to improve rate performance.

In yet another approach, fluoride precursors (e.g., metal oxides, metal hydroxides, or metal nanoparticles) may be used with HF, F₂Or a solution of a fluorinating agent to form fluoride directly within the framework pores. The precursors can be introduced into the framework by solution infusion, wetting of the framework with a precursor suspension, vapor permeation of the volatile Me compounds (capillary condensation), and other routes. In thatAfter infusion of the fluoride precursor, the scaffold may be exposed to HF vapor, F in the case of insoluble fluoride formation₂Or the action of an HF solution. In many cases, the fluorinating agent can be dissolved in an organic solvent such that the fluoride formed remains within the framework pores.

In the relatively volatile metal fluorides (e.g., SbF)₅、SbF₃、BiF₅、SnF₂And other metal fluorides), filling the framework with active material may be performed by capillary condensation of fluoride vapors. Because of capillary action, the vapor preferentially concentrates into the framework capillaries, starting with the smallest pores-the interaction of the smallest pores with the vapor is strongest. Because the generally desired framework pore size may be on the nanometer scale (e.g., about 1nm to about 10nm), a very selective state of intra-pore concentration can be achieved, thereby avoiding any concentration on the outer surface of the framework or in larger pores.

In yet another approach, fluoride nanoparticles (including porogen formed by condensation of nanoparticles) may be first produced and then infiltrated with a precursor of the scaffolding matrix material. In certain examples, a polymer or mixture of polymers (or copolymers) may be used as a precursor to the backbone matrix. Upon thermal treatment, the precursor may be converted into a porous conductive skeletal matrix. As described in more detail for various types of fluorides and particle-containing scaffolding matrices, the outer protective coating can further encapsulate the resulting fluoride-containing composite particles.

The matrix material may be filled with various active materials depending on the particular application. The combination of the above methods accordingly provides the ability to achieve a wide range of desired compositions and morphologies of the active particles within the matrix.

The porosity of the scaffolding matrix need not be uniform. Further, in certain example designs, the relative change in average pore fraction from the center of the particle to the surface conductive matrix may provide unique advantages. For example, having a larger pore volume in the center (or bulk) of the particle may allow for larger MF loadings and higher energy densities. At the same time, having a smaller pore volume near the surface of the particles may provide improved mechanical stability to the composite particles. It also helps to form a more stable and more form-fitting protective coating. Such a coating may penetrate into at least some of the pores of the MF-infiltrated scaffolding matrix.

Fig. 4A-4B are graphical depictions (different distributions of pore volume) showing four specific examples of porous skeletal matrices, with the average pore fraction of the matrices varying in relative variation from the center of the particle to the surface. In the design of fig. 4A, the bulk of the pore volume is more or less uniform in the bulk of the particle, but is greatly reduced near the surface layer. In the design of fig. 4B, the porosity of the matrix material gradually decreases from the center of the particle to the surface of the particle. In the design of fig. 4C, the top surface layer may comprise different morphologies and compositions. Two or more layers may be present in the vicinity of the surface in order to achieve improved performance, wherein the layer near the surface may comprise a larger pore volume than the top surface layer. In the design of fig. 4D, the near-surface layer may include a smaller pore volume than the top surface layer. In this case, the protective coating may first seal the MF-infiltrated matrix particles in the near surface layer, while the larger pores of the top surface layer may prevent sintering of the particles during coating formation.

Fig. 5 shows a schematic diagram illustrating the charge and discharge process within the (single) pores, wherein lithium ions react with the fluoride confined within the pores, thereby forming nanoclusters consisting of fluoride forming elements and nanoclusters of LiF. In the illustrated example, the composite is cycled between (i) a first state including pores 502 (e.g., less than about 6nm) and fluoride (MFx)504 within pore walls 506 and (ii) a second state including clusters 508 of fluoride-forming elements (M) distributed with LiF510 within pore walls 506.

Even when fluoride-forming elements are produced (e.g., in CuF)₂In the case of Cu) are not connected to each other, they remain in a range near the electron channel of the conductive pore wall. Thus, the electrons required for the reaction of equation 1 may be provided by the conductive matrix. In addition, the kind of the reaction substance is limitedClusters of improved F element (in CuF) made in the pore walls₂In the case of Cu) with LiF, which improves the rate of the electrochemical reaction (as shown by equation 1). Finally, the interaction with the pore walls may reduce dissolution of the cathode active material into the electrolyte.

The formation of chemical bonds between fluoride clusters and pore walls may be beneficial in certain designs. For example, such bonds limit the movement of LiF and fluoride-forming element clusters within the pores during cell operation, thereby improving the long-term stability of the fluoride pore matrix composite. Such bonds may be formed during penetration of the fluoride into the porous matrix in which the functional groups are dispersed and may involve other species-such as oxygen and sulfur atoms.

In certain applications, the reaction of fluoride or fluoride-forming elements (e.g., metals) with the electrolyte may result in undesirable side reactions-such as oxidation of the electrolyte, formation of gases, or dissolution of the fluoride-forming elements into the electrolyte due to chemical or electrochemical corrosion. Electrolyte decomposition can form a film, which can prevent or slow reversible switching during cell operation. The formation of gaseous species may cause undesirable cell swelling and otherwise diminish the rate capability of the cell. Dissolution or corrosion of the active material elements reduces the cathode capacity. To overcome this problem, the protective layer discussed above may be wrapped around the fluoride-impregnated porous matrix core in a form-fitting manner, thereby avoiding direct contact between the electrolyte solvent species and the fluoride and fluoride-forming elements. The surface diffusion of lithium ions is generally faster than their diffusion within the bulk of the material. In some cases, the lithium ion diffusion into/out of the fluoride porous matrix composite is fast enough to allow the cell to operate at a sufficiently fast rate (for a given application), although the pores are devoid of electrolyte. In this case, the outer surface area of the scaffolding matrix may be used for deposition of the ion-conducting (and solvent-impermeable) shell, thereby sealing the active material deposited within the scaffolding matrix and avoiding common undesired contact of the active material with solvent molecules of the electrolyte.

Fig. 6A-6B show two specific examples of fluoride-containing composites, in which active fluoride nanoparticles or active fluoride nanoplatelets are confined within a conductive matrix of a nanoporous material, and in which all fluoride-matrix composite particles are further coated with a protective layer of shell material that is conductive to lithium ions but impermeable to electrolyte solvents. In each of the illustrated example designs, the composite particle includes pores 602 (e.g., less than about 10nm), conductive pore walls 604 of the particle core, fluoride 606 infiltrated within the pores 602 of the particle core, and a corresponding shell — e.g., an "active" shell 610 that is impermeable to the electrolyte solution and consists of other active (lithium ion storage) but intercalation-type materials for multiple purposes, or an "inactive" shell 612 that is impermeable to the electrolyte solvent (but permeable to lithium ions) and protects the fluoride from undesired reactions with the electrolyte.

In certain examples, the protective shell material may comprise one of the following types of materials: an oxide, oxyfluoride, sulfide, fluorosulfide, oxysulfide, fluoride, non-fluorine halide, nitride, oxynitride, hydride, polymer, or carbon.

In more detail, fig. 6A shows an example of a fluoride-containing composite material having an "active" material shell that is also capable of storing lithium ions during discharge of a lithium or lithium-ion battery. Fig. 6B shows an example of a fluoride-containing composite with an overall "inactive" material shell that cannot store more than, for example, 50mAh/g of Li over the voltage range to which the fluoride matrix composite particles are exposed during battery operation. In certain applications, it may be advantageous for the shell material to have a relatively small volume change during insertion and extraction of lithium ions. Thus, in the case of a protective shell being an "active" material, it may be advantageous for such a material to store lithium ions by intercalation within the potential range at which the cathode operates, since intercalation reactions typically involve relatively small volume changes.

In some cases, it may be advantageous to make the protective case "multifunctional" by: (ii) has the ability to transport lithium ions while preventing transport of solvent molecules to the fluoride-containing core, (ii) has the additional function of storing lithium ions (used as active material) within the operating potential range (as previously illustrated by fig. 6A), (iii) provides an additional mechanical enhancement function (to help minimize volume changes within the particle during lithium ion insertion), and (iv) improves conductivity (including a conductive outer layer-such as a conductive polymer layer, a conductive carbon layer, a conductive metal layer, or a conductive oxide layer).

In some cases, it may be advantageous for the protective shell to be a composite material. The shell may be a composite material comprising at least an inner layer and an outer layer, with one or more further layers between the inner and outer layers. The shell can accordingly be made by combining different coatings and providing different layers to provide different functions. For example, one component of the shell may provide better structural strength and another component provides better electrical conductivity. In another example, one component may provide better ionic conductivity and the other provides better electrical conductivity. In certain applications, it may be advantageous to have these components penetrate each other. In this case, if one component has better electrical conductivity and the other has better ionic conductivity, the composite shell may provide high ionic conductivity and electrical conductivity.

Further, a portion of the cellular scaffolding matrix of the core may be exposed and thus may be used for stable attachment of the (polymeric) adhesive. The polymeric adhesive may also be securely attached to the protective shell. A more stable particle binder interface may provide more stable performance of the electrode.

Fig. 7A-7B illustrate two specific examples of fluoride-containing composites having a protective shell layer that is a composite material, according to various embodiments. As with the example design of fig. 6, each of the illustrated example designs herein includes a composite particle comprising pores 602 (e.g., less than about 10nm), conductive pore walls 604 of the particle core, and fluoride 606 infiltrated within the pores 602 of the particle core. Additionally, each of the illustrated example designs herein includes a respective composite shell-e.g., a "permeable" composite shell 710, or a combination of an outer protective shell layer 712 and an inner protective shell layer 714, the "permeable" composite shell 710 being an embedded composite material that is impermeable to electrolyte solvents and is infused within a porous framework based on conductive material, the outer protective shell layer 712 being composed of, e.g., an embedded material, and the inner protective shell layer 714 being a composite material of fluoride infused within a porous framework of conductive material.

In more detail, fig. 7A shows a form-fitting shell composed of an intercalation-type active material (e.g., lithium metal oxide or lithium metal phosphate) infiltrated with a porous conductive material (e.g., carbon). Fig. 7B shows a form-fitting shell consisting of two layers: an outer layer of an embedded active material, and (ii) an inner layer of a metal fluoride infiltrated into the electrically conductive porous shell. One advantage of having a fluoride-filled electrically conductive porous shell is that if the pore size in such shell is smaller than the pore size of the porous electrically conductive matrix core, it is easier to "seal it" (make it impermeable to solvent molecules) with a lithium ion conducting material without allowing such material to impregnate the core in large quantities.

In certain applications (e.g., when the particle size is large or when the transport of lithium ions through the electrolyte-free porous fluoride-containing core is slow), it is advantageous to have so-called "channel pores" (e.g., greater than about 6nm) within the fluoride-containing composite particles that enable rapid transport of ions from the exterior of the particles to their core.

Fig. 8 shows two specific examples of fluoride-containing composites according to various embodiments, in which the fluoride conductive core contains relatively small (e.g., less than 6nm) pores that limit fluoride and relatively large "channel" pores (e.g., greater than 6nm) designed to provide rapid transport of ions from the electrolyte solution into the core of the particle. As in the example design of fig. 6, each of the illustrated example designs herein includes a composite particle including pores 602 (e.g., less than about 6nm), conductive pore walls 604 of the particle core, and fluoride 606 infiltrated within the pores 602 of the particle core, with or without a protective shell 610. Additionally, each of the illustrated example designs herein includes a channel pore (e.g., greater than about 6nm) for rapid lithium ion entry into the core.

In more detail, in fig. 8A, the channel pores are not filled with an active material or a solid electrolyte, so that ions are transported in the liquid phase in the pores (i.e., the pores are filled with a liquid electrolyte). In fig. 8B, the channel pores are filled with an active material or a solid electrolyte having high ion conductivity so that ions are transported in the pores by a solid phase manner. In this case, the filled channel pores may provide an additional mechanical enhancement function, further helping the particles to maintain a constant size and avoid cracking during lithium ion insertion and extraction.

In certain applications, it may be advantageous to keep the dimensions of the battery (e.g., the thickness of the pouch-shaped battery) as constant as possible during operation of the battery. However, high capacity electrodes, such as anode particles based on Li alloy type active materials or cathode particles based on conversion type active materials, may have some volume change during the back and forth movement of Li between the anode and cathode. According to a porous skeletal matrix having relatively small volume changes during lithium ion insertion/extraction, certain volume changes may be minimized by using certain methods described herein. However, some volume change may remain in at least one of the electrodes. Such thickness and volume variations may even be intentionally introduced in order to maximize the volumetric energy storage characteristics of the electrode. To further prevent thickness variations at the cell level, the expansion of both electrodes can be adjusted more so as to compensate for the total volume variations and bring them to an acceptable level (e.g., less than 3% in some applications).

In certain designs, it may be advantageous to introduce a gradual change in the concentration of the protective material from the center to the surface of the composite particle. In this case, the overall stability of the particles may be improved. The lack of compositional discontinuities makes it more resistant to particle breakage during handling and electrode preparation. In addition, even with the formation of surface fissures, protection of at least a portion of the individual particles is still effectively performed. A larger fraction of protective material (e.g., embedded active material) near the surface of the particle may help improve particle stability, while a smaller fraction of active material in the center of the particle may help improve particle energy density.

Fig. 9A-9D show four specific examples of MF filled conductive matrix particles additionally comprising a protective material, such as an intercalation-type active material or simply a lithium ion conducting material (which may have a low capacity-e.g., less than about 50mAh/g in the potential range of particle operation in the cell), that prevents undesirable reactions with the electrolyte and improves the stability and performance of the cell. As in the example design of fig. 6, each of the illustrated example designs herein includes a composite particle comprising pores 602 (e.g., less than about 6nm), conductive pore walls 604 of the particle core, and fluoride 606 infiltrated within the pores 602 of the particle core, with or without a protective shell 910, a composite shell 912, an additional coating 914, and the like. Additionally, each of the illustrated example designs herein includes a gradient fill 930 of an embedding type material, which gradient fill 930 may protect the MF from undesired interaction with the electrolyte. In these examples, the volume fraction of MF may be uniform within the scaffolding matrix or vary according to a particular distribution (e.g., having a smaller volume fraction of MF near the surface of the particle).

In more detail, fig. 9A shows the simplest case of MF-infiltrated scaffolding matrix particles gradually filled to protect the coating material. Fig. 9B shows an example of a similar material with an additional layer of thicker protective coating material on the outer surface of the particle. Such a layer may preferably contain as small a fraction of MF as possible. However, certain content of MF may be unavoidable during synthesis. A surface layer of suitable thickness may be in the range of, for example, from about 2nm to about 200 nm. The volume fraction of the embedded material may be compromised, as a larger fraction may result in better stability and higher capacity, while a smaller fraction may result in composite particles having higher energy density. Fig. 9C shows a similar particle, but where the outer layer is a composite material. In certain examples, such a composite material may comprise two or more osmotic components (e.g., a conductive component and a lithium ion storage component), as previously described.

Fig. 9D shows another example where an outer layer of protective shell material may be additionally covered with a functional shell layer. Such layers may have different functions. For example, it may increase the electrical conductivity of the material, improve the interaction with the electrolyte, improve the spreading of the slurry, improve the adhesion to the binder or just further improve the mechanical stability of the particles. The layer should be permeable to the active material ions of interest (e.g., lithium ions in the case of lithium or lithium ion batteries). It may be continuous and form-fitting or non-continuous (e.g., composed of nanoparticles). Conductive polymers (especially those that remain conductive over the potential range at which the electrode operates), conductive carbon (e.g., including carbon with sp generally bound thereto)²Carbon of C atoms of (a), metals (e.g., transition metals such as Fe, Al and other metals, or, for example, rare earth metals or their salts-which salts are generally insoluble in the electrolyte), semimetals (e.g., Si, Sn and other semimetals), metal sulfides (e.g., titanium sulfide, iron sulfide and other metal sulfides), metal fluorides (especially those that do not undergo a conversion reaction in the potential range of operation of the electrode and have low solubility in the electrolyte), metal oxides, and mixtures of the above-discussed materials are examples of suitable compositions for such functional layers.

In certain designs, the protective coating may be formed directly on the surface of a Metal Fluoride (MF) active material dispersed within the conductive scaffolding matrix particles.

Fig. 10A-10B show two examples of a portion of a composite material in which MF is confined within a conductive material pore (e.g., carbon pore) and additionally coated with a protective material coating 1010. As shown, the protective material coating 1010 can be formed as a coating on an MF surface (as shown in fig. 10A) or as a coating of a second MF2 material on a first MF1 material surface (as shown in fig. 10B). The appropriate thickness of such a layer may depend on the size of the pores and the size of the MF particles. By way of example, suitable thicknesses may generally range from between about 0.2 to about 20 nm.

The volume fraction of MF within the skeletal matrix need not be uniform. The reduced volume fraction of MF near the surface of the conductive matrix particles may result in improved mechanical and electrochemical stability of the particles when used in a metal-ion battery.

11A-11B illustrate two specific examples of the average volume fraction that may be occupied by MF in certain embodiments varying along the radius of the particle from the center to the surface of the particle.

In certain designs, the mass or volume fraction of the protective material distribution within the composite particles may also vary from the center to the surface of the composite.

12A-12D illustrate examples of the variation of the average mass fraction of the protective material along the radius of the composite particle. Fig. 12A and 12B show the growth fraction near the surface and the smaller fraction of protective material within the center of the particle. Fig. 12C shows an example where the protective material actually disappears near the center of the particle and is primarily confined to the surface area. Fig. 12D shows an example of uniform distribution of the protective material within the composite material (e.g., when it is applied directly to the surface of the MF particles confined within the pores of the conductive matrix).

As discussed above, the embedded active material may be included in the MF-containing composite particles. In certain examples, such inclusion serves to improve stability of the MF (e.g., to function as a protective layer). In other examples, such an inclusion is used to provide a large current in a pulsed situation. The embedded-type materials generally have higher rate capabilities and therefore their inclusion can allow for large current pulses for the battery supported by the composite electrode. Examples of suitable embedded active materials are indicated above. These intercalation compounds are often divided into a number of crystal structures-such as layered structures, spinel structures, olivine structures and hectorite structures-to name just a few of the most common examples being given above. The layered structure is an intercalation compound of the cathode material in a lithium ion battery and a metal chalcogenide including TiS₃And NbSe₃And has previously been as a possible embeddingCathode materials have been studied. They do not serve as high energy density materials but can provide adequate power performance and protection for the MF. Layered LiCoO₂、LiMnO₂、LiNi_xMn_yCo_zO₂And LiNi_xCo_yAl_zO₂(where x, y and z range from 0 to 1) are more commonly used in devices. Typical examples of spinels include LiCo₂O₄And LiMn₂O₄. Typical examples of olivine active materials include LiFePO₄、LiCoPO₄And LiMnPO₄. Olivine belongs to the broad class of polyanionic compounds. The large polyanions (XO4)3- (X ═ S, P, Si, As, Mo, W) occupy the lattice and these anions, increase the cathode redox potential and stabilize its structure. Non-olivine polyanionic embedded active materials may also be used. Lithium iron hydroxyphosphite is a common example of a non-olivine polyanionic intercalation-type active material. Typical examples of lithiumoxysulfate materials include LiFeSO₄F and LiVPO₄F。

As can be seen by the above examples, most active materials may contain up to about 50 atomic percent oxygen. Some suitable active materials also contain transition metal atoms-including Fe. The use of such elements in the protective material may provide cost advantages due to the low cost of Fe.

When designing a composite comprising an MF and an intercalation-type active material, it may be advantageous to ensure electrochemical stability of the intercalation-type active material over the potential range at which the electrode operates. In certain examples, it may be advantageous for the active material to have the highest capacity over the potential range at which the cathode operates (typically from above 1V for Li/Li + to below 4-4.2V for Li/Li +).

Fig. 13A-13D show four specific examples of MF filled conductive matrix particles additionally including an embedded active material. In these examples, the fraction of the embedded active material varies from the center to the periphery (surface) of the composite particle.

In certain applications, it may be advantageous to use two or more metal fluorides within the composite particles. Certain metal fluorides andreduced solubility when in contact with the electrolyte (at least when used in the potential range of cathode operation), more favorable interaction with the electrolyte (e.g., formation of favorable and stable solid electrolyte interfacial interlayers), formation of an interconnected network of metal nanoparticles during the conversion reaction (so that rate performance can be higher), or other attractive characteristics. At the same time, these metal fluorides may suffer from higher cost or lower energy density (e.g., lower than CuF) than other fluorides₂Energy density of). Combining different types of metal fluorides into one composite material may provide attractive properties-such as a combination of high energy density, high rate, and high stability properties.

Fig. 14A-14C show three specific examples of composite particles comprising a skeletal matrix and two types of metal fluorides (MF1 and MF 2). In fig. 14A, the ratio of the mass fraction of the metal fluoride is uniform within the particle (no change from the center to the periphery of the particle). In fig. 14B and C, there is more MF2 inclusions near the surface of the composite particle.

Fig. 15 shows an example of a building block for a lithium ion battery in which electrodes of varying volume and thickness (e.g., each varying by more than 6% by volume) are carefully designed to offset each other's variations and minimize variations in cell size during their operation. In this example, the cathode cycles between an expanded state 1502 and a compacted state 1504, while the anode cycles between a compacted state 1506 and an expanded state 1508. For example, if the anode increases in thickness by 10% during lithium ion insertion, the porosity and architecture of the cathode particles (e.g., as shown in the porous particles of fig. 2-14) can be adjusted such that the cathode shrinks by 7-13% during Li extraction. In this way, the total volume change remains below 3%.

In certain applications, the use of a solid electrolyte or solid electrolyte layer may provide the benefit of improved stability.

Fig. 16 shows a specific example of an electrode comprising a conductive scaffolding matrix infiltrated into a nanoporous material, wherein the electrode is further coated with a solid electrolyte layer, or the solid electrolyte completely infiltrates the pores between the individual fluoride-containing composite particles. As shown, the electrode may include a current collector 1602, composite fluoride-containing active particles 1604 having relatively very small (e.g., less than about 15%) volume changes during lithium ion insertion and extraction, and a solid electrolyte layer 1606 coating the electrolyte particles. Because the matrix reduces the volume change within the composite particles (compared to the volume change of a conventional MF), these composite particles may provide improved stability when combined with a solid electrolyte in a battery cell.

In many of the figures discussed above, the shape of the particles is shown as being approximately spherical. In some applications, the use of irregularly shaped particles may reduce powder manufacturing costs.

Fig. 17 shows a specific example of irregularly shaped active particles containing fluoride impregnated in a conductive nanoporous matrix. As in the example design of fig. 6, the illustrated example design here includes a composite particle comprising pores 1702 (e.g., less than about 10nm), electrically conductive pore walls 1704 of the particle core, and fluoride 1706 infiltrated within the pores 1702 of the particle core. In other applications, the use of columnar, fibrous, or platelet particles may provide certain benefits (e.g., higher electrical interconnectivity within the electrode, or higher packing density).

In certain designs, it may be advantageous to use porous skeletal matrix particles having pores greater than 10 nm. Larger pores may be easier to fill with fluoride uniformly.

Fig. 18A-18D show four specific examples that may still be attractive using skeletal particles with large pores. For example, pores as large as 500nm may be used in certain designs. However, their performance may be compromised. In the illustrated example design, each pore contains fluoride 1802 infiltrated within conductive pore walls 1804 and, in distinction, includes a conductive coating 1806, conductive particles 1808, and/or conductive segments 1810 that can encapsulate fluoride clusters (nanoparticles).

In more detail, fig. 18A shows macropores in which clusters of metal fluoride are coated with a thin (preferably, less than about 1nm) layer of conductive material (e.g., carbon) in order to provide the electrically insulating fluoride-including LiF pathways needed for reversibility of electron transport to the electrochemical reaction (see equation 1).

Fig. 18B shows an example in which fluoride clusters (nanoparticles) contain conductive nanoparticles (having various shapes or compositions). The conductive particles may comprise metals, conductive carbon, conductive ceramic particles, and other substances. In this case, electrons can be conducted from one conductive nanoparticle to another to participate in the electrochemical reaction. Such particles can also serve another function-reducing the mobility of the fluoride-forming element and LiF so that the two materials remain close to each other so that reversible electrochemical reactions can proceed faster. Yet another potential function of such particles is to catalyze the electrochemical reaction to lower the potential barrier, and thus lower the overpotential, thus increasing the energy efficiency of the cell and increasing the operating voltage (and thus increasing the energy density). In addition, the reduction of the energy barrier of these transitions improves the rate performance and power characteristics of the battery.

Fig. 18C shows an example where a fluoride cluster (nanoparticle) contains nanoparticles (having at least one of the three functions described above) and a surface coating that can improve conductivity or reduce mobility of the reaction product, or both.

Fig. 18D shows an example where multiple fluoride clusters (nanoparticles) form a composite with a conductive material (e.g., carbon) and such a composite is confined within these larger pores. In this example, electrons will be transported through the conductive portion of such a composite (e.g., through carbon if carbon is used to form the composite).

FIG. 19 includes a flow chart illustrating an exemplary method of making a metal fluoride containing composite electrode. In this example, the manufacturing method includes: providing an active fluoride material to store and release ions during operation of the cell, wherein the storage and release of ions results in a substantial change in volume of the active material (block 1902); and (ii) forming a nanoporous, electrically conductive scaffolding matrix within which the active fluoride material is disposed, wherein the scaffolding matrix structurally supports the active material, electrically interconnects the active material, and accommodates volumetric changes in activity (block 1904). In certain designs, forming the skeletal matrix may include, for example, forming a carbon-containing precursor, oxidizing and carbonizing the carbon-containing precursor to form carbonized particles, and activating the carbonized particles at an elevated temperature to form the skeletal matrix having a pore volume greater than 50% by volume. In certain designs, the active fluoride material infused scaffolding matrix may be formed, for example, as a powder containing particles, wherein the method further comprises mixing the active fluoride material infused scaffolding matrix particles with a binder and casting the binder-bound particles onto the metal foil current collector. In certain designs, the method may further include forming a shell at least partially encasing the active fluoride material and the scaffolding matrix, the shell substantially permeable to ions stored and released by the active material. In some designs, at least a portion of the shell material may be deposited by chemical vapor deposition. In certain designs, at least the exterior of the shell may be electrochemically deposited during one or more initial cell cycles during which electrochemical decomposition of at least some electrolyte components occurs.

For some designs, the protective coating may be deposited from the vapor phase by a vapor deposition process. Examples of such methods include, but are not limited to, Chemical Vapor Deposition (CVD), Atomic Layer Deposition (ALD), plasma enhanced ALD, plasma enhanced CVD, vapor permeation, and other methods. For some designs, the protective material may be deposited by solution. Examples of suitable methods include sol-gel, layer-by-layer deposition, polymer adsorption, surface initiated polymerization, nanoparticle adsorption, spray drying, and other methods.

FIGS. 20A-20B include a flow chart illustrating another exemplary method of making a metal fluoride containing composite electrode. In this example, the method of making includes: providing a porous conductive matrix (e.g., in powder form) (block 2002); (ii) infiltrating the substrate (e.g., particles) with a metal fluoride active material (block 2004); (iii) (optionally) depositing an embedded active material within the matrix (optional block 2006); (iv) optionally depositing a protective coating on the accessible surface of the metal fluoride (optional block 2008); (v) (optionally) depositing a metal ion (e.g., lithium ion) conductive protective coating on the surface of the composite particle, thereby forming closed pores that are inaccessible to electrolyte solvent molecules (optional block 2010); (vi) optionally depositing a functional coating on the surface of the composite particles (optional block 2012); and (vii) (optionally) mixing the composite (particles) with a binder and depositing on the current collector substrate, thus producing a composite particle-based electrode (optional block 2014).

The protective coating may be formed not only before the electrode is formed but also after the electrode is formed (but before the battery is assembled). The coating may be deposited by vapor deposition methods (e.g., as described above), by solution deposition methods (e.g., as described above), by electroplating deposition, by electroless deposition, and by other well-known methods of coating deposition.

21A-21B include a flow chart illustrating another exemplary method of making a metal fluoride containing composite electrode. In this example, the method of making includes: providing a porous conductive matrix (e.g., in powder form) (block 2102); (ii) infiltrating the substrate (e.g., particles) with a metal fluoride active material (block 2104); (iii) (optionally) depositing an embedded active material within the matrix (optional block 2106); (iv) optionally depositing a protective coating on the accessible surface of the metal fluoride (optional block 2108); (v) (optionally) depositing a functional coating on the surface of the composite particle (optional block 2110); (vi) (optionally) mixing the composite material (particles) with a binder and depositing on a current collector substrate, thereby producing a composite particle-based electrode (optional block 2112); and (vii) (optionally) depositing a metal ion (e.g., lithium ion) conductive protective coating on the accessible surface of the composite electrode, forming closed pores within the composite that are inaccessible to electrolyte solvent molecules (optional block 2114).

The protective coating may also be formed in situ after assembly of the battery cell. In such a case, the reduction (or oxidation, or both) product of at least one component of the electrolyte on the surface of the electrolyte particles during the first cycle (at low temperature, at room temperature, or at elevated temperature (e.g., 30-80 ℃)) may result in the formation of a suitable protective layer permeable to active metal ions (e.g., lithium ions in the case of a lithium or lithium ion battery). In certain examples, the formation of a suitable coating may be catalyzed by the addition of salt additives to the electrolyte or by surface species on the surface of the composite particles. In certain examples, rare earth element-containing salt additives (e.g., La-containing salt additives), halogen-containing salt additives (e.g., I-or F-containing additives), and sulfur-containing salt additives may be well-suited for forming protective coatings.

FIGS. 22A-22B include a flow chart illustrating another exemplary method of making a metal fluoride containing composite electrode with a protective coating formed in situ after cell assembly. In this example, the method of making includes: providing a porous conductive matrix (e.g., in powder form) (block 2202); (ii) infiltrating the substrate (e.g., particles) with a metal fluoride active material (block 2204); (iii) (optionally) depositing an embedded active material in the matrix (optional block 2206); (iv) optionally depositing a protective coating on the accessible surface of the metal fluoride (optional block 2208); (v) (optionally) depositing a functional coating on the surface of the composite particle (optional block 2210); (vi) mixing (optionally) composite material (particles) with a binder and depositing on the current collector substrate, thereby producing a composite particle-based electrode (optional block 2212); (vii) providing an electrolyte capable of forming a lithium ion-permeable (and generally solvent-impermeable or transition metal ion-impermeable) layer during one or more electrochemical cycles; and (viii) assembling a battery cell comprising the produced electrode and a suitable electrolyte, and forming a protective layer in situ by changing the electrochemical potential of the metal fluoride electrode (block 2216).

Conventional cells typically operate with 0.7-1.3M electrolyte. If an organic electrolyte is used in a battery cell with an MF conductive matrix composite, a suitable salt concentration of metal ions (e.g., lithium ions) can range from about 0.1M up to about 12M. In particular, ultra-high molar concentrations of electrolytes (e.g., 3-12M, which can be achieved in electrolytes without salt precipitation) can significantly improve the stability of these composites (especially if the protective coating is absent or imperfect) by significantly reducing the dissolution of metal fluorides during cycling. It may be particularly advantageous to employ an electrolyte having a lithium ion salt with a melting energy higher than that of the metal ion or metal-containing ion (which may be generated in the metal fluoride during the conversion reaction).

In certain designs, one or more of the fluoride-containing components described above may contain Li.

In certain designs, it may be advantageous to pre-lithiate the metal fluoride electrode prior to use in a rechargeable lithium or lithium ion battery cell. A number of suitable methods have been found. These methods include, but are not limited to: direct contact with a Li metal or Li metal alloy component, (ii) chemical lithiation, and (iii) electrochemical lithiation. For electrochemical lithiation, Li is inserted from the electrolyte into the fluoride-containing electrode while current is applied. Insertion of lithium ions is accompanied by replenishment of the cation Li from other Li-containing electrodes (e.g., Li foils) into the electrolyte or by formation of a reducing species (e.g., in gas, liquid or solid form) at the counter electrode (from the counter anion).

The process of electrochemical lithiation can also be performed within a pre-assembled or fully assembled battery cell. In this case, the third electrode (except for the anode and the cathode) may be used as the Li source. The third electrode may preferably contain more Li. In one example, a Li foil (e.g., a surface-protected Li foil) may be used as such a sacrificial electrode in order to supply lithium ions for lithiation. In some applications, such a third electrode may be (almost) completely consumed.

The description of the present invention is provided to enable any person skilled in the art to make or use the embodiments of the present invention. It is to be understood, however, that the invention is not limited to the particular forms, process steps, and materials disclosed herein, as various modifications of these embodiments will be apparent to those skilled in the art. That is, the general principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.