阅读说明：本技术 基于石墨烯的一次化学电流源 (Graphene-based primary chemical current source ) 是由 安德烈·瓦列列维奇·切格拉科夫 丹尼斯·尤列维奇·科尔尼洛夫 马克·米哈伊洛维奇·盖勒 谢尔盖 于 2019-12-23 设计创作，主要内容包括：本发明属于电气工程领域。一次化学电流源是金属氧化碳电化学系统中基于石墨烯的一类新的能量饱和的不可充电化学电流源,其中基于石墨烯类材料的纳米结构材料用作电流形成组件阴极,由于各种含氧官能团的存在,能够与阳极活性材料的离子(例如,锂、钠、镁、钙、钾)形成不可逆的化合物,因此具有增加的放电容量电流形成过程(放电)。技术成果是提高一次化学电源的耗电量特性。(The invention belongs to the field of electrical engineering. Primary chemical current sources are a new class of energy-saturated, non-rechargeable chemical current sources based on graphene in metal-carbon oxide electrochemical systems, where graphene-based materials based nanostructured materials are used as current-forming component cathodes, capable of forming irreversible compounds with ions of the anode active material (e.g., lithium, sodium, magnesium, calcium, potassium) due to the presence of various oxygen-containing functional groups, thus having an increased discharge capacity current-forming process (discharge). The technical result is to improve the power consumption characteristics of the primary chemical power source.)

1. A primary chemical source of electric energy comprising a housing in which at least one anode, at least one cathode, at least one electrolyte, a current collector and a separator are mounted, characterized in that a nano-structured material based on graphene-like material is used as current-forming element of the cathode.

2. The primary chemical power source according to item 1, characterized in that graphene oxide is used as the graphene-based material.

3. The primary chemical power source according to item 1, characterized in that fluorinated graphene is used as the graphene-based material.

4. The primary chemical power source according to item 1, characterized in that chlorinated graphene is used as the graphene-based material.

5. The primary chemical power source according to item 1, characterized in that brominated graphene is used as the graphene-based material.

6. The primary chemical power source according to item 1, characterized in that graphene nitrate is used as the graphene-based material.

7. The primary chemical power source according to item 1, characterized in that graphene sulfate is used as the graphene-based material.

8. The primary chemical power source according to item 1, characterized in that a mixture of the compounds listed in items 2 to 7 is used as the graphene-based material.

9. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and carbon nanotubes is used as the graphene-based material.

10. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and an oxidation product of carbon nanotubes is used as the graphene-based material.

11. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and graphite is used as the graphene-based material.

12. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and an oxidation product of graphite is used as the graphene-based material.

13. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and a carbon quantum dot is used as the graphene-based material.

14. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and an oxidation product of a carbon quantum dot is used as the graphene-based material.

15. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and carbon black is used as the graphene-based material.

16. The primary chemical power source according to item 1, characterized in that a composite material based on an oxidation product of one or more compounds listed in items 2 to 7 and carbon black is used as the graphene-based material.

17. The primary chemical power source according to item 1, characterized in that a composite material based on one or more compounds listed in items 2 to 7 and activated carbon is used as the graphene-based material.

18. The primary chemical power source according to item 1, characterized in that a composite material based on an oxidation product of one or more compounds listed in items 2 to 7 and activated carbon is used as the graphene-based material.

19. A primary chemical source of electrical energy according to item 1, characterized in that said nanostructured material is used in the form of: a powder having a particle size of 0.05 to 300 μm; a gel and aerogel having a porosity of 15% to 99.1%, or mixtures thereof; a film having a thickness of 0.01 to 500 micrometers; fibers having a length of 0.05 to 50 microns and a diameter of 0.01 to 5 microns; hollow spheres having a diameter of 0.02 to 200 microns and a sphere wall thickness of 0.002 to 0.04 microns, or mixtures thereof.

Technical Field

The invention belongs to the field of electrical engineering, and generates a novel graphene-based energy-saturated primary (non-chargeable) chemical current source (CPS).

Prior Art

A variety of primary chemical sources of electrical energy are known from the prior art (see table 1), (chemical current sources: reference/edited by n.v. korovin and a.m. skudinn-moscow: MEI press, 2003, page 138) which have the major drawback of a specific energy consumption not exceeding 650Wh/kg, which narrows the applicability of this type of power source.

The closest analog of the claimed invention is a source of primary chemical current comprising a carbonaceous cathode material-a polymonochlorohydrocarbon of the general formula (CF) n (i.a. kevrinskii et al lithium current source-moscow, 1992, page 143).

A disadvantage of the primary chemical current source of such lithium-fluorocarbon (CF) n systems is their low discharge energy capacity, not exceeding 400 Wh/kg.

Summary of the invention

Primary chemical current sources are a new class of energy-saturated, non-rechargeable chemical current sources based on graphene in metal-carbon oxide electrochemical systems, where graphene-based materials based nanostructured materials are used as current-forming component cathodes, capable of forming irreversible compounds with ions of the anode active material (e.g., lithium, sodium, magnesium, calcium, potassium) due to the presence of various oxygen-containing functional groups, thus having an increased discharge capacity current-forming process (discharge).

Technical task

The invention aims to create a primary chemical current source with high specific power consumption characteristics. The technical result of the invention is to improve the power consumption characteristic of the primary chemical power supply.

Task resolution

The specified technical result is achieved by the proposed primary chemical current source being a new class of energy-saturated non-chargeable chemical current sources based on graphene in metal-carbon oxide electrochemical systems, wherein graphene-based nanostructured materials-due to the presence of various oxygen-containing functional groups, are able to form irreversible compounds with ions of the anode active material (e.g. lithium, sodium, magnesium, calcium, potassium) during current formation, thus having a material process (discharge) of increased discharge capacity.

The specified technical result is realized by the following modes: the graphene-based primary chemical power source consists of a housing in which at least one anode, at least one cathode, at least one electrolyte, a current collector and a separator are mounted, wherein according to the invention a nanostructured material based on graphene-like materials is used as the current forming component of the cathode.

As the graphene-based material, there can be used: graphene, graphite oxide, reduced graphite oxide, fluorinated graphene, reduced fluorinated graphene, chlorinated graphene, reduced chlorinated graphene, brominated graphene, reduced brominated graphene, nitric graphene, reduced nitric graphene, sulfuric graphene, reduced graphene sulfuric graphene, mixtures of the listed compounds.

Composites based on one or more of the above compounds with carbon nanotubes can be used as graphene-like materials; oxidation products with carbon nanotubes; containing graphite; and graphite oxidation products; with carbon quantum dots; oxidation products with carbon quantum dots; ash exists; soot-containing oxidation products; activated carbon is used; oxidation products with activated carbon.

Composites based on one or more of the above compounds with metal microparticles and nanoparticles capable of forming irreversible compounds with ions of the anode active material can be used as graphene-like materials.

The nanostructured materials can be used in the following forms: a powder having a particle size of 0.05 to 300 microns; a gel and aerogel having a porosity of 15% to 99.1%, or mixtures thereof; a film having a thickness of 0.01 to 500 micrometers; fibers having a length of 0.05 to 50 microns and a diameter of 0.01 to 5 microns; hollow spheres having a diameter of 0.02 to 200 microns and a sphere wall thickness of 0.002 to 0.04 microns, or mixtures thereof.

Brief description of the drawings

FIG. 1 shows: a) an optical digital micrograph of graphene spheres; b) scanning electron microscope photomicrographs of the graphene spheres.

FIG. 2 shows: a) appearance of reduced graphene oxide films; b) scanning electron micrographs of reduced graphene oxide film cuts.

Fig. 3 shows a scanning electron micrograph of tin nanoparticles on the surface of reduced graphene oxide flakes.

Fig. 4 shows a scanning electron microscope micrograph of graphene aerogel microparticles.

Carry out the description of the protocol

The following representative examples demonstrate the practical feasibility of the present invention.

Example 1

Based on massHighly dispersed composite material of graphene oxide powder (particle size 15 to 30 μm) and soot (particle size 25 to 50 μm) in a% ratio of 2: 1 was used as current formation the cathode component of the primary chemical current source was mixed with surfactant (sodium dodecyl sulfate, 0.5g/1g mixture) and water (2ml) and dispersed using an ultrasonic device. The obtained cathode current-forming component was mixed with a binder, sodium carboxymethyl cellulose (5% by weight of the current-forming component), and the obtained paste was coated on an aluminum foil having a thickness of 100 to 300 μm, and dried and rolled to a thickness of 60 to 180 μm. Next, a cut of the electrode having a size of 2, 5X 1,5cm was made. The cathode obtained in this way is contained in a standard assembly of primary chemical sources of electrical energy, in which 1M LiPF is used₆The solution in ethylene carbonate/dimethyl carbonate (1: 1) was used as the electrolyte, lithium metal as the anode, the separator was a polypropylene film with a porosity of 30% and a thickness of 15 microns, the body was made of laminated aluminium. When discharged at 0.02 to 0.2mA in an operating voltage range of 3.5 to 1.5V, the element exhibited a capacity of 6 to 14mAh, which was 400 to 5500mAh/g in terms of the mass of a current forming component of a cathode of a chemical power supply device.

Example 2

The hollow graphene ball powder (shown in figure 1) with the diameter of 10-100 microns and the wall thickness of 0.005-0.02 microns is used as a current forming component of a primary chemical power supply cathode. To manufacture a cathode for a chemical power supply device, hollow graphene spheres were mixed with a binder dissolved in advance in N-methyl-2-pyrrolidone-polyvinylidene fluoride (5% by mass of a current-forming component), and then the resulting paste was coated on an aluminum foil having a thickness of 100 to 300 μm, and dried and rolled to a thickness of 60 to 180 μm. Next, a cut of the electrode having a size of 2, 5X 1,5cm was made. The cathode obtained in this way is contained in a standard assembly of primary chemical sources of electrical energy, in which 1M LiPF is used₆The solution in ethylene carbonate/dimethyl carbonate (1: 1) was used as the electrolyte, lithium metal as the anode, the separator was a polypropylene film with a porosity of 30% and a thickness of 15 microns, the body was made of laminated aluminium. When discharged at 0.02 to 0.2mA in an operating voltage range of 3.5 to 1.5V, the element showed a capacity of 6-14mAhThe amount is converted into the mass of current forming components of the cathode of the chemical power supply device, and the capacity is 400 to 5500 mAh/g.

Example 3

A reduced graphene oxide thin film (see fig. 2a) with a thickness of 0.1 to 1 μm (see fig. 2b) was used as a current forming component of the primary chemical current source cathode. To manufacture a chemical power device cathode, a reduced graphene oxide thin film is deposited on the surface of an aluminum foil, and then heat-treated at a temperature of 70 to 180 ℃ in a hydrogen atmosphere. Meanwhile, no binder is used in manufacturing the cathode of the chemical power supply device. Next, a cut of the electrode having a size of 2, 5X 1,5cm was made. The cathode obtained in this way is contained in a standard assembly of primary chemical sources of electric energy, in which NaClO is used₄The solution in ethylene carbonate/dimethyl carbonate (1: 1) was used as the electrolyte, lithium metal as the anode, the separator was a polypropylene film with a porosity of 30% and a thickness of 15 microns, the body was made of laminated aluminium. When discharged at 0.02 to 0.2mA in an operating voltage range of 3.5 to 1.5V, the element exhibited a capacity of 3 to 9mAh, which was 450 to 4800mAh/g in terms of mass of a current forming component of a cathode of a chemical power supply device.

Example 4

Highly dispersed composites based on reduced graphene oxide and tin nanoparticles are used as current forming components for the cathode of a primary chemical current source. The powder having a particle size of 200 to 250 μm is composed of reduced graphene oxide flakes coated with tin nanoparticles (see fig. 3) having a particle size of 0.005 to 0.01 μm. In order to manufacture a cathode for a chemical power supply device, a current-forming component is mixed with a binder (5% by weight of the current-forming component) dissolved in N-methyl-2-pyrrolidone-polyvinylidene fluoride, and then the resulting paste is coated on an aluminum foil having a thickness of 100 to 200 μm, followed by heat treatment at 70 to 180 ℃ in a hydrogen atmosphere and rolling to a thickness of 60 to 120 μm. Next, a cut of the electrode having a size of 2, 5X 1,5cm was made. The cathode obtained in this way is contained in a standard assembly of primary chemical sources of electrical energy, in which 1M LiPF is used₆The solution in ethylene carbonate/dimethyl carbonate (1: 1) is used as electrolyte, lithium metal as anode, and the separator is polypropyleneA membrane with a porosity of 30% and a thickness of 15 microns, the body being made of laminated aluminium. When discharged at 0.01 to 0.1mA in an operating voltage range of 3.5 to 1.5V, the element exhibited a capacity of 4 to 16mAh, which was 650 to 5500mAh/g in terms of the mass of a current forming component of a cathode of a chemical power supply device.

Example 5

Graphene aerogel particles with an average size of 2 μm were used as the current forming component of the primary chemical current source cathode (see fig. 4). To manufacture a cathode for a chemical power supply device, a current-forming component was mixed with a binder dissolved in N-methyl-2-pyrrolidone-polyvinylidene fluoride (5% by mass of the current-forming component), and the resulting paste was coated on an aluminum foil having a thickness of 100 to 200 μm, dried and rolled to a thickness of 60 to 120 μm. Next, a cut of the electrode having a size of 2, 5X 1,5cm was made. The cathode obtained in this way is contained in a standard assembly of primary chemical sources of electrical energy, in which 1M LiPF is used₆The solution in ethylene carbonate/dimethyl carbonate (1: 1) was used as the electrolyte, lithium metal as the anode, the separator was a polypropylene film with a porosity of 30% and a thickness of 15 microns, the body was made of laminated aluminium. When discharged at 0.02 to 0.2mA in an operating voltage range of 3.5 to 1.5V, the element exhibited a capacity of 9 to 24mAh, which was 650 to 5500mAh/g in terms of the mass of the current forming component of the cathode of the chemical power supply unit.

The technical result of the claimed invention is therefore a high unit power consumption of the primary chemical source, in excess of 650 watt-hours/kg.

Analysis of the background art shows that the set of essential features provided in the formulation of the invention is unknown. This enables us to conclude that the technical solution applied satisfies the conditions of "novelty" of patentability.

Comparative analysis shows that no solution was found in the background art for features matching the significant features of the claimed invention, nor was it confirmed that these features would affect the technical results. Therefore, the applied technical scheme meets the conditions of patentability and creativity.

Table 1: primary source of chemical current

INDUSTRIAL APPLICABILITY

The above information confirms the possibility of using the claimed graphene-based primary chemical current source, which can be used in the field of electrical engineering, thus meeting the requirements of patentability "industrial applicability".