阅读说明：本技术 具有高电压阴极的电化学电池 (Electrochemical cell with high voltage cathode ) 是由 J·B·高德伊娜弗 M·H·S·S·德奥利维拉布拉嘎 于 2018-04-03 设计创作，主要内容包括：本公开提供了可再充电的电化学电池,其包括电解质侧、阴极侧和聚合物/增塑剂。所述电解质侧包括固态玻璃电解质和阳极,所述固态玻璃电解质包含电解质可迁移阳离子和电偶极子,并且所述阳极包含电解质可迁移阳离子的金属并在阳极：固体玻璃电解质界面处与固体玻璃电解质接触。阴极侧包括的阴极,该阴极含有阴极活性材料,可逆地提取/插入所述阴极活性材料中。阴极活性材料相对于锂(Li)金属的电压为3V至15V。聚合物/增塑剂在固体玻璃电解质：聚合物/增塑剂界面处与固体玻璃电解质接触,并在聚合物/增塑剂：阴极界面处与阴极接触,从而在电化学电池的充电和放电期间,将阴极客体阳离子限制在阴极侧,并且将电解质可迁移阳离子限制在阳极侧。(The present disclosure provides a rechargeable electrochemical cell comprising an electrolyte side, a cathode side, and a polymer/plasticizer. The electrolyte side includes a solid glass electrolyte comprising electrolyte migratable cations and an electric dipole, and an anode comprising a metal of the electrolyte migratable cations and having: the solid glass electrolyte is in contact with the solid glass electrolyte at an interface. The cathode side includes a cathode containing a cathode active material reversibly extractable/insertable into the cathode active material. The voltage of the cathode active material with respect to lithium (Li) metal is 3V to 15V. Polymer/plasticizer in solid glass electrolyte: a polymer/plasticizer interface with a solid glass electrolyte and a polymer/plasticizer ratio at the polymer/plasticizer interface: the cathode interface is in contact with the cathode, thereby confining cathode guest cations to the cathode side and electrolyte migratable cations to the anode side during charge and discharge of the electrochemical cell.)

1. A rechargeable electrochemical cell, comprising:

an electrolyte side comprising:

a solid glass electrolyte comprising electrolyte migratable cations and an electric dipole; and

an anode comprising a metal from which cations can be transported by an electrolyte and in contact with the solid glass electrolyte at an anode-solid glass electrolyte interface;

a cathode side comprising a cathode containing a cathode active material in which cathode guest cations are reversibly extracted/inserted, the cathode active material having a voltage of 3V to 15V with respect to lithium (Li) metal; and

a polymer/plasticizer in contact with the solid glass electrolyte at a solid glass electrolyte to polymer/plasticizer interface and in contact with the cathode at a polymer/plasticizer to cathode interface, thereby confining cathode guest cations to the cathode side and electrolyte migratable cations to the anode side during charge and discharge of the electrochemical cell.

2. The rechargeable electrochemical cell of claim 1, wherein the electrolyte migratable cations and cathode guest cations are the same type of cation.

3. The rechargeable electrochemical cell of claim 1, wherein the electrolyte migratable cations and cathode guest cations are different types of cations.

4. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises a migratable cation.

5. The rechargeable electrochemical cell of claim 4, wherein the migratable cations in the polymer/plasticizer are the same type of cations as the electrolyte migratable cations, the cathode guest cations, or both.

6. The rechargeable electrochemical cell of claim 4, wherein the migratable cations in the polymer/plasticizer are different types of cations than electrolyte migratable cations, cathode guest cations, or both.

7. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises a material having a dielectric constant of 50 to 24000.

8. The rechargeable electrochemical cell of claim 4, wherein the polymer/polymer plasticizer comprises a polymer or plasticizer and the molar ratio of polymer or plasticizer to migratable cation is from 10:1 to 50: 1.

9. The rechargeable electrochemical cell of claim 4, wherein said migratable cations are made of LiClO in a polymer/plasticizer₄And (4) supplying.

10. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises-C ≡ N terminal groups.

11. The rechargeable electrochemical cell of claim 10, wherein the polymer/plasticizer comprises succinonitrile.

12. The rechargeable electrochemical cell of claim 1, wherein said polymer/plasticizer comprises an electric dipole.

13. The rechargeable electrochemical cell of claim 1, further comprising a cathode current collector in contact with the cathode at a cathode-to-cathode current collector interface.

14. The rechargeable electrochemical cell of claim 1, wherein the electrolyte migratable cations, cathode guest cations, or both move in the direction of the anode or cathode current collector by an average of no more than 1/10,000 times the distance between the anode solid glass electrolyte interface and the cathode current collector interface during charge/discharge cycles of the electrochemical cell.

15. The rechargeable electrochemical cell of claim 1, wherein the metal in the anode comprises: li metal, sodium (Na) metal, potassium (K) metal, aluminum metal (Al), magnesium (Mg) metal, or alloys thereof.

16. The rechargeable electrochemical cell of claim 1, wherein the electrolyte migratable cations comprise: lithium ion (Li)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Aluminum ion (Al)³⁺) Or magnesium ion (Mg)²⁺)。

17. The rechargeable electrochemical cell of claim 1, wherein the cathode active material comprises a layered oxide, spinel, or olivine.

18. The rechargeable electrochemical cell of claim 1, wherein the cathode guest cations comprise: lithium ion (Li)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Aluminum ion (Al)³⁺) Or magnesium ion (Mg)²⁺)。

19. The rechargeable electrochemical cell of claim 1, wherein the cathode further comprises elemental carbon (C).

20. The rechargeable electrochemical cell of claim 1, wherein the electric dipole of the solid glass electrolyte comprises a compound of formula a₂X or AX^-Or MgX or Al₂X₃Wherein A is Li, Na or K, and X is oxygen (O), sulfur (S) or a combination thereof.

21. The rechargeable electrochemical cell of claim 1, wherein the solid glass electrolyte further comprises a dipolar additive.

22. The rechargeable electrochemical cell of claim 1, wherein the relative permittivity (e) of the solid glass electrolyte_r) Is 10²To 10⁵。

23. The rechargeable electrochemical cell of claim 1, wherein the solid glass electrolyte has an ionic conductivity (σ) at 25 ℃. (σ ℃_i) Is 10^-2S/cm to 10^-3S/cm。

24. The rechargeable electrochemical cell of claim 1, wherein the rechargeable electrochemical cell has a specific capacity of 2500mAh/g of cathode active material to 5000mAh/g of cathode active material at 25 ℃.

25. The rechargeable electrochemical cell of claim 1, wherein the specific capacitance of the rechargeable electrochemical cell continuously increases between 1 and 20,000 charge/discharge cycles.

26. A battery comprising at least one electrochemical cell as claimed in any one of the preceding claims.

27. A battery as claimed in claim 26, comprising at least two electrochemical cells as claimed in any one of claims 1 to 25.

28. A battery pack according to claim 26 or claim 27 for powering an all-electric or hybrid vehicle.

29. A battery pack as claimed in claim 26 or claim 27 for use in powering a hand-held tool or an electronic device.

30. A battery as claimed in claim 26 or claim 27, for use in powering a ship or submarine.

31. A battery pack as claimed in claim 26 or claim 27 for use in powering a drone, aircraft or other flying toy or vehicle.

32. The battery pack of claim 26 or claim 27 for storing electrical energy in a stationary storage in a home, business, hospital and/or electricity grid.

33. A battery as claimed in claim 26 or claim 27 for storing electrical energy generated by solar radiation, wind, waves, hydroelectric power and/or nuclear power.

Technical Field

The present disclosure relates to a rechargeable electrochemical cell in which the electrolyte includes two dielectric electronic insulators in series and the cathode may be a high voltage cathode. The present disclosure also relates to devices that use these electrochemical voltages, such as rechargeable batteries (batteries) and supercapacitors.

Background

An electrochemical cell has two electrodes, an anode and a cathode separated by an electrolyte. Electrochemical cells can have a variety of functions, including use as battery cells, capacitor cells, or fuel cells. Electrochemical cells generally have two electrodes, an anode and a cathode, which are good electronic conductors and store electrical energy as chemical energy in battery cells and surface electrostatic energy in capacitor cells. The catalytic electrode converts the chemical energy of the fuel into electrical energy in the fuel cell. The electrochemical cell also contains an electrolyte positioned in series between the anode and the cathode.

During charging or discharging of an electrochemical cell, a reaction between two electrodes involves the transport of positive charge within the electrochemical cell between the two electrodes. During charging and discharging, negative charges are transported in the external circuit as electron currents. The electrolyte is an electronic insulator, so negative charges are forced to be transported through the external circuit; it cannot be transported internally through the electrolyte.

In conventional rechargeable electrochemical battery cells, both electrodes are a source and sink of migratable cations (often referred to as working ions) of the electrolyte. During charging, one electrode serves as a source of working ions and the other electrode serves as a sink; during discharge, these functions are reversed during discharge.

In conventional electrochemical capacitor cells, electrostatic energy (electrostatic power) is stored as electrical energy in two electric double layer capacitors at the interface of two electrodes, the electrolyte.

Disclosure of Invention

The present disclosure provides a rechargeable electrochemical cell comprising an electrolyte side, a cathode side, and a polymer/plasticizer. The electrolyte side includes a solid glass electrolyte comprising electrolyte migratable cations and an electric dipole, and an anode comprising a metal of the electrolyte migratable cations and having: the solid glass electrolyte is in contact with the solid glass electrolyte at an interface. The cathode side includes a cathode containing a cathode active material from which cathode guest cations are reversibly extracted/intercalated. The voltage of the cathode active material with respect to lithium (Li) metal is 3V to 15V. Polymer/plasticizer in solid glass electrolyte: a polymer/plasticizer interface with a solid glass electrolyte and a polymer/plasticizer ratio at the polymer/plasticizer interface: the cathode interface is in contact with the cathode, thereby confining cathode guest cations to the cathode side and electrolyte migratable cations to the anode side during charge and discharge of the electrochemical cell.

The above electrochemical cell may also have one or more of the following additional features, which may be combined with each other in any and all possible combinations, unless expressly excluded from each other:

i-i) the electrolyte migratable cation and the cathode guest cation can be the same type of cation;

i-ii) the electrolyte migratable cation and the cathode guest cation can be different types of cations;

ii) the polymer/plasticizer may include a migratable ion;

ii-a) the migratable cations in the polymer/plasticizer can be the same type of cation as the electrolyte migratable cation, the cathode guest cation, or both;

ii-b) the migratable cations in the polymer/plasticizer can be different types of cations from the electrolyte migratable cations, the cathode guest cations, or both;

ii-c) the polymer/plasticizer may comprise a polymer or plasticizer, and the molar ratio of polymer or plasticizer to migratable cation may be from 10:1 to 50: 1;

ii-d) the migrateable cations can be derived from LiClO in the polymer/plasticizer₄Providing;

iii) the polymer/plasticizer may include materials having a dielectric constant of 50 to 24,000;

iv) the polymer/plasticizer may comprise-C ≡ N end groups;

iv-a) the polymer/plasticizer may include succinonitrile;

v) the polymer/plasticizer may comprise an electric dipole;

vi) the electrochemical cell can include a cathode current collector in contact with the cathode at a cathode-cathode current collector interface;

vi-a) during charge/discharge cycles of the electrochemical cell, the electrolyte migratable cations, the cathode guest cations, or both, can move in the direction of the anode or cathode current collector by an average of no more than 1/10,000 the distance between the anode solid glass electrolyte interface and the cathode current collector interface;

vii) the metals in the anode may include: li metal, sodium (Na) metal, potassium (K) metal, aluminum (Al) metal, magnesium (Mg) metal, or an alloy thereof;

viii) the electrolyte migratable cations can include: lithium ion (Li)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Aluminum ion (Al)³⁺) Or magnesium ion (Mg)²⁺)；

ix) the cathode active material may include a layered oxide, spinel, or olivine;

x) the cathode guest migratable cations can include: lithium ion (Li)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Aluminum ionSeed (Al)³⁺) Or magnesium ion (Mg)²⁺)；

xi) the cathode may comprise elemental carbon (C);

xii) the electric dipole of the solid glass electrolyte may comprise a general formula A₂X or AX^-Or MgX or Al₂X₃Wherein A is Li, Na or K, and X is oxygen (O), sulfur (S) or a combination thereof;

xiii) the solid glass electrolyte may comprise a dipolar additive;

xiv) relative dielectric constant (. epsilon.) of solid glass electrolyte_r) May be 10²To 10⁵；

xv) ion conductivity (σ) of solid glass electrolyte at 25 deg.C_i) May be 10^-2S/cm to 10^-3S/cm；

xvi) the rechargeable electrochemical cell can have a specific capacity at 25 ℃ of from 2500mAh/g of cathode active material to 5000mAh/g of cathode active material;

xvii) the specific capacitance of rechargeable electrochemical cells continues to increase between 1 and 20,000 charge/discharge cycles.

The present disclosure also provides a battery (battery) comprising at least one electrochemical cell as described above or at least two electrochemical cells as described above. These battery packs may be used to power fully electric or hybrid vehicles, to power hand-held tools or electronic devices, to power boats or submarines, to power drones, airplanes or other flying toys or vehicles, to store electrical energy in a fixed storage in the home, business, hospital and/or power grid, or to store electrical energy generated by solar radiation, wind, wave, hydro-power generation and/or nuclear energy.

The electrochemical cells and batteries described above may also be combined with any of the other features described in this specification or the drawings, which features may be combined with each other unless expressly excluded from each other.

Brief description of the drawings

For a more complete understanding of the present disclosure, and the features and advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, which illustrate examples of the disclosure and, unless explicitly mutually exclusive, may be combined with each other and with all other written or illustrated portions of the disclosure.

Fig. 1 is a schematic cross-sectional view of an electrochemical cell of the present disclosure upon discharge.

Fig. 2 is a schematic cross-sectional view of a solid glass electrolyte, polymer/plasticizer, cathode active material particles, carbon particles, and current collector of an electrochemical cell of the present disclosure upon discharge.

Fig. 3 is a schematic view of a solid glass electrolyte comprising cellulose.

Fig. 4 is an exploded schematic view of a button cell containing a solid glass electrolyte according to the present disclosure.

Fig. 5 is a graph showing the combined nyquist curves for three electrochemical cells. In accordance with the present disclosure, an electrochemical cell contains a solid glass electrolyte and a polymer/plasticizer (labeled "having a glass electrolyte and a plasticizer"). An electrochemical cell contains a liquid glass electrolyte and a polymer/plasticizer (labeled "1M LiPF with plasticizer₆(EC/DEC 1:1 "in v/v). The remaining electrochemical cell contained liquid glass electrolyte and no polymer/plasticizer (labeled "having 1 MLiPF)₆(EC/DEC 1:1 "in v/v).

Fig. 6A is a plot of charge/discharge voltage as a function of electrochemical cell capacity for the number of cycles shown in an electrochemical cell containing a liquid electrolyte but no polymer/plasticizer.

Fig. 6B is a graph of cycle number as a function of charge and discharge capacity in an electrochemical cell containing a liquid electrolyte without a polymer/plasticizer.

Fig. 6C is a plot of charge/discharge voltage as a function of electrochemical cell capacity for the number of cycles shown in an electrochemical cell containing a liquid electrolyte and a polymer/plasticizer.

Fig. 7A is a plot of charge/discharge voltage as a function of electrochemical cell capacity for the number of cycles shown in an electrochemical cell containing a solid electrolyte and a polymer/plasticizer.

Fig. 7B is another graph of charge/discharge voltage as a function of electrochemical cell capacity for the number of cycles shown in an electrochemical cell containing a solid electrolyte and a polymer/plasticizer.

Fig. 7C is a plot of charge/discharge voltage as a function of electrochemical cell capacity for the first cycle and the 316 th cycle in an electrochemical cell containing a solid electrolyte and a polymer/plasticizer.

Figure 7D is a graph of cycle number as a function of charge and discharge capacity in an electrochemical cell containing a solid electrolyte and a polymer/plasticizer.

Fig. 7E is a graph of cycle number as a function of charge and discharge capacity in an electrochemical cell containing a solid electrolyte and a polymer/plasticizer.

Detailed Description

The present disclosure relates to electrochemical cells, for example, rechargeable battery cells or supercapacitor cells, that store electrical energy as chemical and electrostatic internal energies through a configuration that includes two dielectric insulators, a solid glass electrolyte, and a polymer/plasticizer. During discharge, these electrochemical cells deliver electrical energy as a current at a voltage (V) for a period of time. The time that the electrochemical cell delivers electrical energy depends on the amount of stored electrical energy and the rate of discharge.

The electrochemical cells disclosed herein can be rechargeable, safe, low cost, and have high energy density, long cycle life, and low internal resistance.

The present disclosure relates to an electrochemical cell comprising two dielectric components, a solid glass electrolyte and a polymer/plasticizer, for example, as shown in fig. 1-3.

Referring now to fig. 1 and 2, an electrochemical cell 10 can include an anode 20 that can include a metal, such as Li metal, Na metal, K metal, aluminum (Al) metal, magnesium (Mg) metal, or alloys thereof. Specifically, the metal may be an alkali metal, for example, lithium (Li), sodium (Na), or potassium (K), or an alloy thereof. The metal in the anode 20 is present as electrolyte migratable cations 210 in the solid glass electrolyte 30. The anode 20 may also include a current collector material, for example, carbon, Al metal, or Mg metal (not shown). The metal in the anode 20 includes at least one metal that is electrochemically active in the electrochemical cell 10, and if more complex electrochemical characteristics are provided, such as the ability to operate at different voltages, the anode 20 may include more than one metal that is electrochemically active in the electrochemical cell 10. The metal may be in the form of a sheet, such as a foil.

The anode 20 may be adjacent to and interface with an anode current collector (not shown) on one side and adjacent to and interface with the solid glass electrolyte 30 on the other side. The anode current collector may also be a metal, such as Stainless Steel (SS) or copper (Cu), and specifically it may be a housing, such as housing 110 shown in fig. 4. The anode 20 is in electronic contact with an anode current collector (if present). In some electrochemical cells 10, the anode 20 may be used without an anode current collector, such as particularly where the anode 20 comprises Al.

Electrochemical cell 10 also includes a cathode 50. Cathode 50 can include any cathode active material 230 having a host framework from which migratable cathode guest cations 250 can be reversibly extracted/inserted. Suitable cathode guest cations 250 include alkali metal cations (e.g., Li)⁺Ion, Na⁺Ions and K⁺Ions), or other metal cations (e.g., Al)⁺Ions and Mg⁺Ions) or larger cations formed from two or more atoms.

Cathode 50 may be a high voltage cathode because it produces a high voltage current when the electrochemical cell is discharged. For example, the high voltage cathode may have a cathode active material and a voltage relative to Li metal of at least 3V, at least 4V, at least 5V, 3V to 15V, 3V to 10V, 3V to 8V, 4V to 15V, 4V to 10V, 4V to 8V, 5V to 15V, 5V to 10V, or 5V to 8V. The discharge voltage of the electrochemical cell can be in any of the ranges described above. High voltages can also be generated at high currents. The cathode active material 230 may be receptive to Li⁺Ions or other cathode guest cations 250. For example, it may be a layered oxide having a crystal structure similar to that of lithium cobaltate, for example, of the formula AMO₂Wherein a is a cathode guest cation and M is a metal or combination of metals, and specifically may include at least one transition metal. The cathode active material 230 may be a spinel having a crystal structure similar to that of lithium cobaltate, for example, of the general formula AM₂O₄Wherein a is a cathode guest cation and M is a metal or combination of metals, and specifically may include at least one transition metal. The cathode active material 230 may be of the general formula AMXO₄Wherein a is a cathodic guest cation, M is a metal or a combination of metals and may in particular comprise at least one transition metal, and X is phosphorus, silicon, sulphur or vanadium. The above formula for the cathode active material 230 can include varying amounts of metals or other components such that all of its compounds have charge neutrality when the cathode guest cation 250 is fully inserted. The cathode active material 230 can also be any other host compound that allows for reversible insertion/extraction of the cathode guest cations 250. In the example shown in fig. 1 and 2, the cathode active material 230 allows Li⁺Reversible extraction/insertion of ions and exist in lithiated (230a) and delithiated (230b) states, both of which may be present in the cathode 50 at the same time. The cathode active material 230 may be in the form of particles, as shown. Cathode 50 may include elemental carbon (C)220, for example, in the form of particles as shown. The elemental carbon may be in the form of carbon black, carbon nanoparticles, carbon fibers, graphite, or other forms of carbon. Cathode 50 also includes a cathode current collector 60. The cathode current collector may include any metal, such as aluminum (Al).

The polymer/plasticizer 40 may be in contact with the solid glass electrolyte 30 at one interface and in contact with the cathode 50 at another interface. The polymer/plasticizer 40 may be a sheet between the solid glass electrolyte 30 and the cathode 50, it may coat the cathode 50, or it may be in any other form suitable for confining the cathode guest cations 250 in the vicinity of the cathode 50, such that the polymer/plasticizer 40 prevents the cathode guest cations 250 from being supplied from the cathode 50 to the anode 20 or the solid glass electrolyte 30 during cycling of the electrochemical cell 10.

The solid glass electrolyte 30 is referred to as glass because it is amorphous, as evidenced by the absence of crystalline material characteristic peaks in X-ray diffraction.

In particular, the solid glass electrolytes of the present disclosure can be glasses containing migratable metal cations, such as alkali metal cations (e.g., Li)⁺Sodium ion (Na)⁺) Potassium ion (K)⁺) Or other metal cations (e.g., aluminum ions (Al))³⁺) Or magnesium ions (Mg)²⁺)). The metal cations are referred to as electrolyte migratable cations 210 and can be cations of the electrochemically active metal in the anode 20 such that the electrolyte migratable cations can plate onto the anode and the electrochemically active metal in the anode 20 can form the electrolyte migratable cations 20. The solid glass electrolyte 30 also contains an electric dipole 240 (e.g., A)₂X or AX^-Or MgX or Al₂X₃Where a ═ Li, Na, or K, and X is oxygen (O), sulfur (S), or a combination thereof), or another element or an electric dipole molecule. Suitable Solid glass electrolytes and methods for their preparation have been described previously in WO2015128834[ Solid electrolyte glass for conducting Lithium or Sodium ions (A Solid electrolyte glass for Lithium or Sodium Ion reduction)]WO2016205064[ Water-soluble Glass/Amorphous Solid Ionic Conductors ]]And WO2018013485[ Self-Charging and/or Self-cycling electrochemical Cells (Self-Charging and/or Self-cycling electrochemical Cells)]The disclosures of the solid glass electrolyte compositions, methods of making them, and methods of incorporating them into electrochemical cells are incorporated herein by reference.

The solid glass electrolyte 30 contains a compound represented by the general formula Q_yX_zOr Q_y-1X_z ^-qOr a polar chain of a combination of two agglomerated dipoles represented by the general formula (I), wherein Q is an alkali metal, e.g., Li, Na and K, Mg or Al, or a combination thereof, and X is an anion or an anion-forming element orCompounds including S, O, silicon (Si) Or Hydroxyl (OH)^-) Or a combination thereof; 0<z ≦ 3 (more specifically, z is 1, z is 2 and/or z is 3), y is sufficient to ensure the general formula A_yX_zOf the dipole, or of the formula A_y-1X_z ^-qOf the dipole (more specifically, 0)<y ≦ 3, or y is 1, y is 2, or y is 3, or a combination thereof), and 1 ≦ q ≦ 3 (more specifically, q is 1, q is 2, or q is 3, or a combination thereof).

After initial charging or initial cycling of electrochemical cell 10, in particular, there may be a charge having the general formula Q_yX_zOr Q_{y- 1}X_z ^-qBecause the additive may lose one or more metal cations while still retaining at least one metal cation bound to an anion, the mixture of dipolar additives of (1) still retains its dipole properties.

A particular dipolar additive may have the formula Q₂S or QS^-Or a combination of two additives of the formula, where Q is Li, Na and/or K, e.g. Li₂S or Li₂S and LiS^-A mixture of (a).

Other specific dipolar additives may have the formula Q₂O or QO^-Or a combination of two additives of the formula, where Q is Li, Na and/or K, e.g. Li₂O or Li₂O and LiO^-A mixture of (a).

Other specific dipolar additives may be ferroelectric condensed molecules of the above dipoles (ferroelectric condensed molecules), where Q is Li, Na or K, and X is O, S or a combination thereof.

Other specific dipole additives may be larger polymeric dipole molecules or compositions, e.g. paper or other cellulose with negative groups, e.g. hydroxyl groups, or Polytetrafluoroethylene (PTFE). Fig. 3 shows a solid glass electrolyte 30 containing cellulose.

Other additives may increase the dielectric constant of the solid glass electrolyte 30. Other additives may include, for example, crystalline materials having a high dielectric constant, and in particular,the dielectric constant is at least 5000, at least 7000, or 5000 to 10000, 7000 to 10000, 5000 to 15000, or 7000 to 15000. Suitable crystalline materials include BaTiO₃、SrTiO₃、CaCu₃Ti₄O₁₂、SiO₂And/or TiO₂。

The presence of the electric dipole provides a high dielectric constant for the solid glass electrolyte 30, for example at least 5000, at least 7000, or 5000 to 10000, 7000 to 10000, 5000 to 15000, or 7000 to 15000.

Furthermore, the solid glass electrolyte 30 is not reduced when in contact with the electrochemical chemical material of the anode 20. Therefore, a passivated Solid Electrolyte Interphase (SEI) is not formed at the interface of the solid glass electrolyte 30 and the anode 20.

The surface of the solid glass electrolyte 30 is wetted by the electrochemically active metal (e.g., alkali metal) of the anode 20, which allows metal to plate from the electrolyte-migratable cations 210 of the solid glass electrolyte 30 to the anode 20 in a dendrite-free manner. This provides for low resistance of metal cation transport across the anode-solid glass electrolyte interface between at least 1000 cycles, at least 2000 cycles, at least 5000 cycles, 200 to 300 cycles, 200 to 1000 cycles, 200 to 5000 cycles, 200 to 10,000 cycles, 200 to 15,000 cycles, 200 to 20,000 cycles, 1000 to 5000 cycles, 1000 to 10,000 cycles, 1000 to 15,000 cycles, or 1000 to 20,000 cycles.

The solid glass electrolyte 30 may have a large dielectric constant, e.g., at least 10²、0²To 10³、10²To 10⁴、10²To 10⁵Relative dielectric constant (. epsilon.) of_r). The ionic conductivity (σ) of electrolyte-transferable cations 210 of solid glass electrolyte 20 at 25 ℃_i) May be at least 10^-2S/cm, or 10^-2S/cm to 10^-3S/cm. This conductivity is comparable to the ionic conductivity of flammable conventional organic liquid electrolytes used in lithium ion batteries. The resistance to cation transport in the solid electrolyte is thickness/[ sigma ]_ixArea of]Wherein σ is_iIs the cation conductivity of the electrolyteAnd the thickness/area is the ratio of the thickness of the electrolyte relative to its area. Typically, the solid glass electrolyte 30 has a thickness/area of less than 1, less than 0.5, less than 0.25, less than 0.1, less than 0.05, 0.01 to 0.1, 0.1 to 0.25, 0.01 to 0.5, 0.01 to 1, 0.05 to 0.1, 0.05 to 0.25, 0.05 to 0.5, 0.05 to 1, 0.1 to 0.25, 0.1 to 0.5, or 01 to 1. For example, σ for the electrochemical cell 10 when measuring resistance by electrochemical electrical impedance spectroscopy or charge/discharge measurements using a symmetric cell with two alkali working ion electrodes_iDetermined by thickness/area.

The solid glass electrolyte 30 is electrically insulating due to a sufficiently large energy state gap and may be non-flammable.

The solid glass electrolyte 30 may be prepared by mixing a mixture containing electrolyte migratable cations 210 or component precursors thereof (typically containing O, OH and C)^-And/or halide-bound working ions) into a cationically-conducting glass/amorphous solid. The process can also be carried out in the presence of a dipolar additive.

The solid glass electrolyte 23 may be in the form of a film, which is typically mechanically robust.

The components of the electrochemical cell 10 may have thicknesses measured perpendicular to the surface area. The thickness of each component may vary by less than 25%, less than 10%, less than 5%, less than 1%, or less than 0.5%, 0.01% to 1%, 0.01% to 5%, 0.01% to 10%, 0.01% to 25%, 0.5% to 1%, 0.05% to 5%, 0.5% to 1%, 0.5% to 5%, 0.5% to 10%, 0.5% to 25%, 1% to 5%, 1% to 10%, 1% to 25%, 5% to 10%, 5% to 25%, or 10% to 25%. The thickness of the solid glass electrolyte may be at least 10 μm, at least 25 μm, at least 50 μm, at least 75 μm, at least 100 μm, 10 μm to 100 μm, 25 μm to 100 μm, 50 μm to 100 μm, 75 μm to 100 μm, 10 μm to 2000 μm, 25 μm to 2000 μm, 50 μm to 2000 μm, 75 μm to 2000 μm, 100 μm to 2000 μm, 10 μm to 5000 μm, 25 μm to 5000 μm, 50 μm to 5000 μm, 75 μm to 5000 μm, or 100 μm to 5000 μm.

The polymer/plasticizer 40 can be any dielectric material formed from a polymer, plasticizer, or combination thereof that is capable of confining the cathode guest cations 250 to the vicinity of the cathode 50 so that the cathode guest cations 250 are not supplied from the cathode 50 to the anode 20 or the solid glass electrolyte 30 during cycling of the electrochemical cell 10. Specifically, the polymer/plasticizer 40 may also be a material that does not oxidize when in contact with the cathode active material 230 during cycling of the electrochemical cell 10. The polymer/plasticizer 40 can have a dielectric constant of at least 50, 50 to 5000, 50 to 10,000, 50 to 15,000, 50 to 20,000, or 50 to 24,000.

The polymer/plasticizer 40 may contain a migratable cation that is different from the cathode guest cation 230 and is limited to the polymer/plasticizer, e.g., a salt. For example, the polymer/plasticizer 40 may contain lithium perchlorate (LiClO)₄). The polymer/plasticizer 40 can accept cations from the cathode 50 without transporting the cathode guest cations 230 to the anode 20 or the solid glass electrolyte. If the polymer/plasticizer includes a migratable cation, the molar ratio of the polymer or plasticizer to the migratable cation can be from 10:1 to 50:1, from 10:1 to 40:1, from 10:1 to 30:1, from 10:1 to 20:1, from 10:1 to 15:1, from 15:1 to 50:1, from 15:1 to 40:1, from 15:1 to 30:1, from 15:1 to 20:1, from 20:1 to 50:1, from 20:1 to 40:1, from 20:1 to 30:1, from 15:1 to 25:1, from 18:1 to 22:1, or from 20: 1.

In particular examples, polymer/plasticizer 40 may include polymers or plasticizers that contain-C.ident.N end groups, including and resembling N.ident.C-CH₂-CH₂-those of C ≡ N.

The polymer/plasticizer 40 may contain point dipoles 270 that may be joined by dipole-dipole interactions, free rotation, or both.

The surface area of the polymer/plasticizer 40 may be the same as or greater than the surface area of the cathode 50 such that the polymer/plasticizer 40 may separate the electrolyte side of the electrochemical cell 10 from the cathode side of the electrochemical cell 10. The surface area of one or more other components of the electrochemical cell 10, including the anode current collector (if present), the anode 20, the cathode 50, and the cathode current collector 60, may be equal to or less than the surface area of the polymer/plasticizer 40. The electrochemical cell 10 may be in a housing or may contain other components to seal the electrochemical cell 10 and allow the polymer/plasticizer 40 to separate the electrolyte side of the electrochemical cell 10 from the cathode side of the electrochemical cell.

The ability of the polymer/plasticizer 40 to block cation transport and its configuration to physically separate the electrolyte side from the cathode side of the electrochemical cell 10 is such that the electrolyte migratable cations 210 are different from the cathode guest cations 250.

During cycling of a conventional electrochemical cell, the cathode expands upon discharge and contracts upon charge. This is particularly true when the cathode is a cathode active material in particulate form. This often leads to failure of conventional electrochemical cells because the cathode active material loosens contact with other components (e.g., solid electrolyte). Liquid electrolytes are commonly used in conventional electrochemical cells to accommodate volume changes in the cathode active material, but liquid electrolytes do not allow the highest voltage achievable with many such cathodes, so the use of a polymer/plasticizer 40 in contact with the cathode 50 in the electrochemical cell 10 of the present disclosure ensures a safe high voltage solid state cell with long cycle life. In electrochemical cell 10, these three-dimensional (3D) volume changes of cathode active material 230 are accommodated by polymer/plasticizer 40, which polymer/plasticizer 40 remains in contact with cathode 50 at its interface during discharge of the electrochemical cell.

Specifically, the high voltage cathode of the electrochemical cell disclosed herein can maintain the particle structure of its cathode active material 230 or the physical structure of other cathode active materials 230, while undergoing distortion changes only when cycling cathode guest cations 250 in and out over a large solid solution range, at best. The volumetric change of cathode active material 230 during cycling can accommodate long cycle life because cathode 50 is in contact with a soft or plastic material (i.e., polymer/plasticizer 40).

As shown in fig. 1, the cathode active material 230 is in the form of particles that are in contact with the polymer/plasticizer 40 on one side and in contact with the cathode current collector 60 on the other side. In the illustration of fig. 2, the cathode active material 230 is in the form of particles that are in contact with the cathode current collector 60 through the carbon particles 200. Other cathode configurations are possible using thicker cathodes in which individual cathode active material particles 230 are in contact with only one of the polymer/plasticizer 40 or the cathode current collector 60, or neither.

The internal resistance of the electrochemical cell 10 can be minimized or reduced to provide a high rate of charge/discharge at room temperature. The cation transport resistance between the electrodes may become a problem due to the low cation conductivity in conventional electrolytes. The present disclosure addresses this problem by limiting the electrolyte migratable cations 210 and cathode guest cations 250 to small displacements. Specifically, during charge/discharge cycles, the electrolyte migratable cations 210, the cathode guest cations 250, or both, can move on average no more than 1/10,000, 1/1000, no more than 1/100, no more than 1/50, from 1/50 to 1/10,000, from 1/50 to 1/1000, from 1/50 to 1/100, from 1/100 to 1/10,000, from 1/100 to 1/1000, or from 1/1000 to 1/10,000 of the distance between the anode, solid glass electrolyte interface, and the cathode, cathode current collector interface.

As shown in fig. 1 and 2, an electric double layer capacitor may be formed at the interface of the solid glass electrolyte 30 and the anode 20, at the interface of the solid glass electrolyte 30 and the polymer/plasticizer 40, and at the interface of the polymer/plasticizer 40 and the cathode 50. The other interface of the polymer/plasticizer 40 and the solid glass electrolyte 30 provides additional electrostatic storage of electrical energy by forming an additional double layer capacitor as compared to an electrochemical cell lacking the polymer/plasticizer.

During discharge of an electrochemical cell 10 that has been charged from a discharged state, by stripping electrolyte migratable cations 210 from anode 20 back into solid glass electrolyte 30, electrolyte migratable cations 210, and small displacements of electric dipole 240 in the electrolyte (including reorientation of electric dipole 240), cations can be migrated by polymer/plasticizer 40 in the polymer/plasticizer ratio of: movement or other contribution at the cathode interface, and intercalation of cathode guest cations 250 extracted during charging of the cathode active material 230b, transport positive charge within the electrochemical cell. Like a conventional electrochemical cell, negative charges are transported by electrons 200 as current in an external circuit (not shown). The discharge involves releasing the polymer/plasticizer stored: electrostatic energy in the capacitor formed at the solid glass electrolyte interface. The discharge of this capacitor is slower than that of conventional capacitors because the polymer/plasticizer: the solid glass electrolyte interface capacitor has no electronic component.

In general, the electrochemical cell 10 containing the solid glass electrolyte 30 operates by transferring charge between the electrodes (anode 20 and cathode 50) using an external circuit (not shown). The displacement of the migrateable cations (210 and 250) transfers ionic charge between the electrodes primarily through small displacements at the electrode interface where plating and stripping can occur. When these small displacements occur, small electric dipole 240 displacements occur in the solid glass electrolyte 30 due to the slower moving electric dipole 240 in the solid glass electrolyte 30 and the presence of electrolyte migratable cations 210. Unlike what typically occurs in liquid electrolytes, these electric dipole displacements largely replace cation transport through the solid glass electrolyte 30. This allows for very rapid charging and discharging and long cycle life of the electrochemical cell 10.

Fig. 1 provides details of the discharge process. Specifically, FIG. 1 shows an electrical double layer capacitor at the anode-solid glass electrolyte interface, where the solid glass electrolyte: another electrical double layer capacitor at the polymer/plasticizer interface and a capacitor at the polymer/plasticizer: another electrical double layer capacitor at the cathode interface. On the anode side of the electrochemical cell 10, the anode 20 returns the electrolyte migratable cations 210 that are stripped from the solid glass electrolyte 30 during discharge, but the electrical double layer capacitor at the anode-solid glass electrolyte interface remains open, as in an uncycled electrochemical cell, to balance the chemical potentials of the two electrodes.

A cathode active material having a specific capacity of the electrochemical cell 10 at 25 ℃ of at least 2500mAh/g, a cathode active material of at least 2750mAh/g, or a cathode active material of at least 3000mAh/g, a cathode active material of from 2500mAh/g to 4000mAh/g, a cathode active material of from 2500mAh/g to 5000mAh/g, a cathode active material of from 2750mAh/g to 3000mAh/g, a cathode active material of from 2750mAh/g to 4000mAh/g, a cathode active material of from 2750mAh/g to 5000mAh/g, a cathode active material of from 3000mAh/g to 4000mAh/g, a cathode active material of from 3000mAh/g, a cathode active material of from 4000mAh/g, a cathode active material of from the cathode active material of from 3000m, Or 3000mAh/g to 5000mAh/g of cathode active material.

The specific capacitance of the electrochemical wire 10 may continuously increase between 1 to 300, 1 to 500, 1 to 1000, 1 to 5000, 1 to 10000, or 1 to 20,000 charge/discharge cycles.

Fig. 4 is a schematic diagram of an exemplary button cell 100 including the electrochemical cell 10 of the present disclosure. The button cell 100 comprises a housing 100, which can be stainless steel or another electronically conductive material or an electronically insulating material with electronically conductive contacts. The housing 110 may serve as an anode current collector. The button cell 100 also includes an anode sheet 120, which anode sheet 120 may include an anode 20 and optionally an anode current collector. The button cell 100 includes a solid glass electrolyte sheet 130, which solid glass electrolyte sheet 130 may include a solid glass electrolyte 30. To facilitate assembly, the solid glass electrolyte sheet 130 may include: a solid glass electrolyte 20 in a paper matrix as shown in figure 3. The button cell 100 also comprises a polymer/plasticizer sheet 140, which polymer/plasticizer sheet 140 comprises a polymer/plasticizer 40. As shown, the polymer/plasticizer sheet 40 has a larger surface area than the solid glass electrolyte sheet 30. The button cell 100 additionally comprises a cathode sheet 150, which cathode sheet 150 comprises the cathode 50 and may also comprise a cathode current collector 60. Finally, the button cell 100 includes a spring 160 to help maintain the interface of the sheets. Button cell 100 can include multiple iterations of sheets 120, 130, 140, and 150 with an electronically insulating separator (not shown) therebetween. One of ordinary skill in the art will appreciate that button cells are often configured as test cells, and that other battery packs may be configured using methods known in the art to accommodate the findings in button cells to other types of battery packs.

Electrochemical cells of the present disclosure (including those electrochemical cells generally described, such as those shown in fig. 1, 2, and 4 or those electrochemical cells described in the examples) may be used in batteries, including both single cell and multi-cell batteries. The battery cell may contain components in addition to such electrochemical cells and a housing or other mechanical features. Multi-cell batteries often contain a plurality of similar battery cells. The battery cells may be manufactured in standard forms, such as button cells (including the button cell of fig. 4), pouch cells, cylindrical wound cells (jellyrollcell), or prismatic cells. They may also take a more custom-made form, such as a custom-made prismatic cell with non-uniform geometry.

The electrochemical cells of the present disclosure may also be used in more complex batteries, such as batteries containing complex circuitry and computer-implemented monitoring and conditioning by processors and memory.

Regardless of simplicity, complexity, or format, all batteries using the electrochemical cells of the present disclosure may exhibit improved safety compared to batteries with liquid electrolytes, particularly with a lower propensity to catch fire when damaged or rapidly charged.

Furthermore, a battery according to the present disclosure may be a multi-cell battery containing at least 10, at least 100, at least 500, 10 to 10,000, 100 to 10,000, 1,000 to 10,000, 10 to 1000, 100 to 1,000, or 500 to 1,000 electrochemical cells of the present disclosure. The cells in a multi-cell battery may be arranged in parallel or in series.

Batteries including the electrochemical cells of the disclosure can be rechargeable and have a life cycle of at least 500 charge/discharge cycles, at least 1,000 charge/discharge cycles, at least 5,000 charge/discharge cycles, at least 10,000 charge/discharge cycles, at least 20,000 charge/discharge cycles, at least 30,000 charge/discharge cycles, 500 to 50,000 charge/discharge cycles, 1,000 to 50,000 charge/discharge cycles, 5,000 to 50,000 charge/discharge cycles, 500 to 30,000 charge/discharge cycles, 1,000 to 30,000 charge/discharge cycles, 5,000 to 30,000 charge/discharge cycles, 500 to 20,000 charge/discharge cycles, 1,000 to 20,000 charge/discharge cycles, or 5,000 to 20,000 charge/discharge cycles.

For example, the electrochemical cells of the present disclosure may be used in portable battery packs, including those used in handheld and/or wearable electronic devices, such as telephones, watches, or laptop computers; in stationary electronic devices, such as desktop computers or mainframe computers; in power tools, such as electric drills; in electric or hybrid land, water or in-hole based vehicles, such as boats, submarines, buses, trains, trucks, cars, motorcycles, mopeds, airplanes, drones, other aircraft and toy versions thereof; for other toys; for energy storage, e.g. for storing electricity from wind, solar, wave, hydroelectric or nuclear power and/or for grid storage; or as a stationary power store for small scale use, e.g. for homes, businesses or hospitals.

Supercapacitor cells may also include electrochemical cells of the present disclosure, and may be particularly useful in applications requiring rapid charging and/or high power, such as electric tools and electric or hybrid vehicles.

Examples

The following examples are provided to further illustrate the principles and specific aspects of the present disclosure. It is not intended, nor should it be construed, to cover all aspects of the disclosure. The features of the following embodiments may be independently combined with any of the features of the electrochemical cells of the present disclosure described in more detail above.