CN116259741A - Sodium-manganese primary cell - Google Patents

Sodium-manganese primary cell Download PDF

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Publication number
CN116259741A
CN116259741A CN202111504703.4A CN202111504703A CN116259741A CN 116259741 A CN116259741 A CN 116259741A CN 202111504703 A CN202111504703 A CN 202111504703A CN 116259741 A CN116259741 A CN 116259741A
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CN
China
Prior art keywords
sodium
primary cell
manganese
electrolyte
carbonate
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CN202111504703.4A
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Chinese (zh)
Inventor
蔡伟
孙操
惠银银
钱家辉
甘朝伦
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Priority to CN202111504703.4A priority Critical patent/CN116259741A/en
Publication of CN116259741A publication Critical patent/CN116259741A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a sodium-manganese primary battery, which uses metal sodium or sodium alloy as a negative electrode, uses manganese dioxide as a main active substance of a positive electrode, and forms a primary battery system with electrolyte and a diaphragm.

Description

Sodium-manganese primary cell
Technical Field
The invention relates to a sodium-manganese primary cell.
Background
Sodium batteries were studied starting in 1960 and high Wen Naliu batteries were first developed. The battery employs molten sodium metal as a negative electrode, molten elemental sulfur as a positive electrode, and a solid electrolyte having sodium ion conductivity as a separator. However, due to the great safety hazards, research on sodium batteries has been focused in recent years on lowering the operating temperature of the batteries. Research work on conventional lithium ion and sodium ion intercalation materials began to draw worldwide attention at the end of the 70 s and the beginning of the 80 s. However, commercialization of sodium ion batteries has not entered a substantial stage due to the lack of suitable anode materials. Sodium resources are abundant and widely distributed, and sodium batteries are considered as ideal candidates for large-scale, low-cost energy storage systems in the future.
Recently, due to its higher theoretical specific capacity (1166 mAhg -1 ) And lower electrode potentials, scientific research interest has been focused on sodium metal negative electrode research. Currently, sodium batteries mainly include sodium-sulfur batteries and sodium-air batteries having sodium metal as a negative electrode, and sodium-ion secondary batteries having hard carbon material as a negative electrode. For example, sodium sulfur (Na-S) cells at room temperature, sodium oxygen (Na-O) 2 ) Batteries and room temperature ZEBRA sodium metal halide batteries. Sodium-sulfur batteries have the advantages of rapid capacity decay, low coulomb efficiency, serious self-discharge and poor practical applicability. Sodium oxygen batteries have problems of metal sodium dendrite growth, electrolyte volatility, flammable components, gas electrode design, and the like. The ZEBRA type sodium metal halide battery has a severe operating temperature, requires a high temperature of 260-300 ℃, and is expensive.
Based on this, it is urgent to study a new sodium battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a sodium-manganese dioxide primary battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a sodium-manganese primary battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises 50-98% by mass of manganese dioxide, 0.05-25% by mass of conductive agent and 0.5-35% by mass of binder; the negative electrode is metal sodium or sodium alloy, and the sodium alloy comprises sodium and at least one element of zinc, magnesium, calcium, silicon, potassium, tin, aluminum and iron; the electrolyte comprises an organic solvent and sodium salt, wherein the sodium salt comprises one or more of sodium hexafluorophosphate, sodium trifluoromethylsulfonate, sodium perchlorate, sodium difluorosulfimide and sodium tetrafluoroborate.
Preferably, the mass percentage of the manganese dioxide in the positive electrode is 80-95%.
Further preferably, the mass percentage of the conductive agent in the positive electrode is 1-10%.
Still more preferably, the mass percentage of the binder in the positive electrode is 1-15%.
Preferably, the conductive agent includes one or more of conductive graphite, conductive carbon black, ketjen black, carbon nanotubes, carbon nanofibers (VGCF).
Preferably, the binder comprises polyvinylidene fluoride (PVDF) and/or Polytetrafluoroethylene (PTFE).
Preferably, the organic solvent comprises one or more of ethylene carbonate, acetonitrile, sulfolane, methyl butyrate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, gamma-butyrolactone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane, 1, 3-dioxane, tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate.
Further preferably, the organic solvent comprises at least propylene carbonate and ethylene glycol dimethyl ether, or the organic solvent comprises at least propylene carbonate and diethylene glycol dimethyl ether.
Preferably, the electrolyte further comprises an additive comprising at least one of vinyl sulfate, vinylene carbonate, 1, 3-propene sultone.
Further preferably, the mass percentage of the additive in the electrolyte is 0.1-10%.
Still more preferably, the additive is 0.3-5% by mass of the electrolyte.
Preferably, the separator includes any one of non-woven fabric, polyethylene (PE), polypropylene (PP), polypropylene/polyethylene/polypropylene (PP/PE/PP).
Preferably, the molar concentration of the sodium salt in the electrolyte is 0.05-2.5 mol/L.
Further preferably, the molar concentration of the sodium salt in the electrolyte is 0.5 to 2mol/L.
Preferably, the shape of the sodium-manganese primary cell comprises any one of button type, cylinder, square and soft package type.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the sodium-manganese primary battery provided by the invention uses metal sodium or sodium alloy as a negative electrode, uses manganese dioxide as a main active substance of a positive electrode, and forms a primary battery system with electrolyte and a diaphragm, and has the advantages of low raw material price and stable discharge platform, and has wide application fields.
Drawings
FIG. 1 is a graph showing the constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 1;
FIG. 2 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 2;
FIG. 3 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 3;
FIG. 4 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 4;
FIG. 5 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 5;
FIG. 6 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 6;
FIG. 7 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 7;
FIG. 8 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 8;
FIG. 9 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 9;
FIG. 10 is a graph of a constant resistance discharge of 1KΩ of the sodium-manganese primary cell prepared in example 10;
in fig. 1 to 10, the abscissa represents the discharge capacity (mAhg) and the ordinate represents the voltage V.
Detailed Description
A sodium manganese primary cell comprising a positive electrode, a negative electrode, a separator, and an electrolyte.
In this application, the positive electrode includes manganese dioxide, a conductive agent, and a binder. Wherein, the mass percentage content of manganese dioxide in the positive electrode is 50-98%, and preferably, the mass percentage content of manganese dioxide in the positive electrode is 80-95%, for example: 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%. The conductive agent includes, but is not limited to, one or more of conductive graphite, conductive carbon black, ketjen black, carbon nanotubes, carbon nanofibers (VGCF). Binders include, but are not limited to, polyvinylidene fluoride (PVDF) and/or Polytetrafluoroethylene (PTFE). In some preferred embodiments, the positive electrode sheet may be directly made of manganese dioxide, a conductive agent, and a binder. Of course, manganese dioxide, a conductive agent and a binder may be mixed and then coated on the current collector to prepare the positive electrode sheet. Current collectors include, but are not limited to, aluminum foil. The material for preparing the anode is low in cost and easy to obtain.
In the application, the negative electrode is metallic sodium or sodium alloy, and the sodium alloy comprises sodium and at least one element of zinc, magnesium, calcium, silicon, potassium, tin, aluminum and iron. The separator may be a single-layer microporous film or a multi-layer composite microporous film or a coated film, and as a preferred example, the separator may be a nonwoven fabric, polyethylene (PE), polypropylene (PP), or polypropylene/polyethylene/polypropylene (PP/PE/PP).
In the present application, the electrolyte includes an organic solvent, a sodium salt, and an additive.
The sodium salt comprises one or more of sodium hexafluorophosphate, sodium trifluoromethane sulfonate, sodium perchlorate, sodium difluorosulfimide and sodium tetrafluoroborate. The molar concentration of the sodium salt in the electrolyte is 0.05 to 2.5mol/L, preferably 0.5 to 2mol/L, for example, 0.5mol/L, 0.6mol/L, 0.7 mol/L, 0.8mol/L, 0.9 mol/L, 1mol/L, 1.1 mol/L, 1.2mol/L, 1.3 mol/L, 1.4 mol/L, 1.5 mol/L, 1.6 mol/L, 1.7 mol/L, 1.8 mol/L, 1.9 mol/L, 2mol/L.
The organic solvent comprises one or more of ethylene carbonate, acetonitrile, sulfolane, methyl butyrate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane, 1, 3-dioxane, tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate. Preferably, the organic solvent includes at least two or more kinds, and when the organic solvent includes two or more kinds, the two organic solvents may be compounded at an arbitrary ratio. Further, the organic solvent at least comprises an ester solvent and an ether solvent, and the ester solvent comprises one or more of ethylene carbonate, methyl butyrate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate; the ether solvent comprises one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane, 1, 3-dioxane and tetrahydrofuran. For example: the organic solvent comprises at least propylene carbonate and ethylene glycol dimethyl ether, or the organic solvent comprises at least propylene carbonate and diethylene glycol dimethyl ether.
The additive comprises at least one of vinyl sulfate, vinylene carbonate and 1, 3-propylene sultone. The mass percentage of the additive in the electrolyte is 0.1-10%, preferably, the mass percentage of the additive in the electrolyte is 0.3-5%, for example: 0.3%, 0.5%, 1%, 1.3%, 1.6%, 1.9%, 2.2%, 2.5%, 2.8%, 3.1%, 3.4%, 3.7%, 4%, 4.5%, 5%, etc.
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The battery in the following examples used a sodium manganese button CR2032 primary battery.
1KΩ normal temperature constant resistance discharge test condition: under normal temperature, the resistance is 1KΩ, and the constant resistance discharges to the cut-off voltage of 2.0V; and testing the discharge performance of the battery by adopting a Shenzhen Xinwei battery tester.
Example 1
Positive plate: 85% manganese dioxide/5% conductive carbon black/10% PTFE, wherein the negative electrode is a metal sodium sheet, the diaphragm is a non-woven fabric diaphragm, and the electrolyte comprises the following components: the organic solvent is propylene carbonate and ethylene glycol dimethyl ether with the mass ratio of 1:1, the electrolyte salt is sodium perchlorate, and the concentration is 1mol/L; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 1.
Example 2
Positive plate: 87% manganese dioxide/5% conductive graphite/8% PTFE, the negative electrode is a metal sodium sheet, the diaphragm is a non-woven fabric diaphragm, and the electrolyte comprises the following components: the organic solvent is ethylene carbonate, propylene carbonate and ethylene glycol dimethyl ether (the mass ratio of the ethylene carbonate to the propylene carbonate to the ethylene glycol dimethyl ether is 8:45:47); electrolyte sodium salt is 0.8mol/L sodium trifluoromethane sulfonate, and additive is 0.5% vinyl sulfate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 2.
Example 3
Positive plate: 90% manganese dioxide/2% carbon nano tube/8% PVDF, the negative electrode is a metal sodium sheet, the diaphragm is a PP/PE/PP composite diaphragm, and the electrolyte comprises the following components: the organic solvent is ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether and sulfolane (the mass ratio of the four is 8:30:47:15); the electrolyte sodium salt is 0.5mol/L sodium difluorosulfimide and 0.1mol/L sodium perchlorate, the additive is 1% vinyl sulfate and 0.3% vinylene carbonate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 3.
Example 4
Positive plate: 90% manganese dioxide/3% VCGF/7% PVDF, the negative electrode is a metal sodium sheet, the diaphragm is a PP/PE/PP composite diaphragm, and the electrolyte comprises the following components: the organic solvent is acetonitrile, propylene carbonate, diethylene glycol dimethyl ether and methyl butyrate (the mass ratio of the four is 8:45:37:10); the electrolyte sodium salt is 0.8mol/L sodium hexafluorophosphate, and the additive is 1%1, 3-propylene sultone; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 4.
Example 5
Positive plate: 91.5% manganese dioxide/1.5% carbon nano tube/7% PVDF, the negative electrode is a metal sodium sheet, the diaphragm is a PP diaphragm, and the electrolyte comprises the following components: the organic solvent is propylene carbonate, ethylene glycol dimethyl ether, 1, 3-dioxolane and sulfolane (the mass ratio of the four is 25:35:25:15); the electrolyte sodium salt is 0.6mol/L sodium perchlorate, the additive is 1.5 percent of 1,3 propylene sultone and 1 percent of vinyl sulfate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 5.
Example 6
Positive plate: 88% manganese dioxide/6% ketjen black/6% PTFE, the negative electrode is a metal sodium sheet, the diaphragm is a non-woven fabric diaphragm, and the electrolyte comprises: the organic solvent is ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether, 1, 3-dioxolane and sulfolane (the mass ratio of the five is 5:25:30:25:15); the electrolyte sodium salt is 0.5mol/L sodium trifluoromethane sulfonate and 0.3mol/L sodium bis (fluorosulfonyl) imide; the additive is 0.5% of vinyl sulfate and 1.3% of 1,3 propylene sultone; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 6.
Example 7
Positive plate: 85% manganese dioxide/6% conductive carbon black/9% PTFE, wherein the negative electrode is a metal sodium sheet, the diaphragm is a non-woven fabric diaphragm, and the electrolyte comprises the following components: the organic solvent is ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether and 1, 3-dioxolane (the mass ratio of the four is 10:20:35:35); the electrolyte sodium salt is 0.5mol/L of sodium difluorosulfimide, 0.1mol/L of sodium perchlorate and 0.1mol/L of sodium tetrafluoroborate; the additive is 0.5% of 1,3 propylene sultone, 0.5% of vinylene carbonate and 1% of vinyl sulfate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 7.
Example 8
Positive plate: 85% manganese dioxide/6% conductive carbon black/9% PTFE, wherein the negative electrode is a metal sodium sheet, the diaphragm is a non-woven fabric diaphragm, and the electrolyte comprises the following components: the organic solvent is ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether and methyl butyrate (the mass ratio of the four is 10:20:35:35); the electrolyte sodium salt is 0.8mol/L sodium trifluoromethane sulfonate, 0.1mol/L sodium perchlorate and 0.1mol/L sodium tetrafluoroborate; the additive is 1% of 1, 3-propylene sultone and 2% of vinyl sulfate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 8.
Example 9
Positive plate: 85% manganese dioxide/6% conductive carbon black/9% PTFE, wherein the negative electrode is a metal sodium sheet, the diaphragm is a non-woven fabric diaphragm, and the electrolyte comprises the following components: the organic solvent is ethylene carbonate, propylene carbonate and ethylene glycol dimethyl ether (the mass ratio of the three is 10:30:60); the electrolyte lithium salt is 1.2mol/L sodium perchlorate, 0.1mol/L sodium hexafluorophosphate and 0.1mol/L sodium tetrafluoroborate; 1.3% of 1,3 propylene sultone and 1% of vinylene carbonate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 9.
Example 10
Positive plate: 88% manganese dioxide/6% conductive graphite/6% PVDF, the negative electrode is a metal sodium sheet, the diaphragm is a PP/PE/PP composite diaphragm, and the electrolyte comprises the following components: the organic solvent is ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether, 1, 3-dioxolane and sulfolane (the mass ratio of the five is 5:20:35:35:5); the electrolyte sodium salt is 0.3mol/L of sodium difluorosulfimide and 0.3mol/L of sodium perchlorate; the additive is 1.5% of 1,3 propylene sultone, 0.5% of vinyl sulfate and 1% of vinylene carbonate; the above materials are assembled into a sodium-manganese button CR2032 primary battery. The constant resistance discharge curve of this example 1KΩ is shown in FIG. 10.
Experimental results
Through the test curve, the positive and negative electrode materials, the electrolyte formula and the sodium-manganese primary battery manufactured by the diaphragm can be normally discharged, and the discharge capacity of the assembled CR2032 button battery is about 120mAh, so that a foundation is provided for the application of the subsequent market.
The present invention has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the same, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. A sodium manganese primary cell, characterized by: the sodium-manganese primary cell comprises an anode, a cathode, a diaphragm and electrolyte,
the positive electrode comprises 50-98% by weight of manganese dioxide, 0.05-25% by weight of conductive agent and 0.5-35% by weight of binder;
the negative electrode is metal sodium or sodium alloy, and the sodium alloy comprises sodium and at least one element of zinc, magnesium, calcium, silicon, potassium, tin, aluminum and iron;
the electrolyte comprises an organic solvent and sodium salt, wherein the sodium salt comprises one or more of sodium hexafluorophosphate, sodium trifluoromethylsulfonate, sodium perchlorate, sodium difluorosulfimide and sodium tetrafluoroborate.
2. The sodium manganese primary cell according to claim 1, wherein: the mass percentage of the manganese dioxide in the positive electrode is 80-95%, the mass percentage of the conductive agent in the positive electrode is 1-10%, and the mass percentage of the binder in the positive electrode is 1-15%.
3. The sodium manganese primary cell according to claim 1, wherein: the conductive agent comprises one or more of conductive graphite, conductive carbon black, ketjen black, carbon nanotubes and carbon nanofibers;
and/or the binder comprises polyvinylidene fluoride and/or polytetrafluoroethylene.
4. The sodium manganese primary cell according to claim 1, wherein: the organic solvent comprises one or more of ethylene carbonate, acetonitrile, sulfolane, methyl butyrate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane, 1, 3-dioxane, tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate.
5. The sodium manganese primary cell according to claim 4, wherein: the organic solvent at least comprises propylene carbonate and ethylene glycol dimethyl ether, or at least comprises propylene carbonate and diethylene glycol dimethyl ether.
6. The sodium manganese primary cell according to claim 1, wherein: the electrolyte further comprises an additive comprising at least one of vinyl sulfate, vinylene carbonate, and 1, 3-propene sultone.
7. The sodium manganese primary cell according to claim 6, wherein: the mass percentage of the additive in the electrolyte is 0.1-10%.
8. The sodium manganese primary cell according to claim 1, wherein: the separator includes any one of non-woven fabric, polyethylene, polypropylene/polyethylene/polypropylene.
9. The sodium manganese primary cell according to claim 1, wherein: the molar concentration of the sodium salt in the electrolyte is 0.05-2.5 mol/L.
10. The sodium manganese primary cell according to any one of claims 1 to 9, wherein: the shape of the sodium-manganese primary battery comprises any one of button type, cylinder, square and soft package type.
CN202111504703.4A 2021-12-10 2021-12-10 Sodium-manganese primary cell Pending CN116259741A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197366A (en) * 1978-08-10 1980-04-08 Hitachi, Ltd. Non-aqueous electrolyte cells
US4419423A (en) * 1980-06-27 1983-12-06 Union Carbide Corporation Nonaqueous cells employing heat-treated MnO2 cathodes and a PC-DME-LiCF3 SO3 electrolyte
JPS60253166A (en) * 1984-05-29 1985-12-13 Sanyo Electric Co Ltd Non-aqueous electrolyte battery
CN109301274A (en) * 2017-07-24 2019-02-01 深圳新宙邦科技股份有限公司 A kind of lithium manganese primary battery
CN111952573A (en) * 2020-08-25 2020-11-17 山东大学 Graphene-manganese dioxide-loaded composite material and preparation method and application thereof
CN112447992A (en) * 2019-08-30 2021-03-05 深圳新宙邦科技股份有限公司 Carbon fluoride-manganese dioxide metal battery electrolyte and battery comprising same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197366A (en) * 1978-08-10 1980-04-08 Hitachi, Ltd. Non-aqueous electrolyte cells
US4419423A (en) * 1980-06-27 1983-12-06 Union Carbide Corporation Nonaqueous cells employing heat-treated MnO2 cathodes and a PC-DME-LiCF3 SO3 electrolyte
JPS60253166A (en) * 1984-05-29 1985-12-13 Sanyo Electric Co Ltd Non-aqueous electrolyte battery
CN109301274A (en) * 2017-07-24 2019-02-01 深圳新宙邦科技股份有限公司 A kind of lithium manganese primary battery
CN112447992A (en) * 2019-08-30 2021-03-05 深圳新宙邦科技股份有限公司 Carbon fluoride-manganese dioxide metal battery electrolyte and battery comprising same
CN111952573A (en) * 2020-08-25 2020-11-17 山东大学 Graphene-manganese dioxide-loaded composite material and preparation method and application thereof

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