CN105140575A - High voltage battery containing aqueous electrolyte - Google Patents

High voltage battery containing aqueous electrolyte Download PDF

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Publication number
CN105140575A
CN105140575A CN201510498772.7A CN201510498772A CN105140575A CN 105140575 A CN105140575 A CN 105140575A CN 201510498772 A CN201510498772 A CN 201510498772A CN 105140575 A CN105140575 A CN 105140575A
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China
Prior art keywords
electrolyte
solution
voltage battery
aqueous electrolyte
battery containing
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Pending
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CN201510498772.7A
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Chinese (zh)
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周飞
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Individual
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Individual
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Priority to CN201510498772.7A priority Critical patent/CN105140575A/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a high-voltage battery containing aqueous electrolyte and a manufacturing method thereof. The battery uses a proper diaphragm to lead the cathode reaction and the anode reaction to occur in different environments, so that the cathode reaction has lower reduction potential and the anode reaction has higher oxidation potential, thereby leading the battery to have higher working voltage. The battery mainly comprises a positive electrode, a negative electrode, positive electrolyte, negative electrolyte and a diaphragm. By reasonably selecting the anode and the cathode, the diaphragm and the electrolyte corresponding to the anode and the cathode, the battery with the working voltage higher than 2.0V can be obtained.

Description

High voltage battery containing aqueous electrolyte
Technical Field
The present invention relates to a battery and a method for manufacturing the same, and more particularly, to a high voltage battery containing an aqueous electrolyte and a method for manufacturing the same.
Background
With the advent of the electronic age, people have increasingly demanded chemical power sources and also increasingly demanded performance. At present, the working voltage of the battery taking an aqueous solution as an electrolyte is almost below 2.0V, and the battery taking an organic solution as an electrolyte has many potential safety hazards. The common carbon zinc battery has low working voltage and low energy density, and the alkaline zinc-manganese battery has relatively excellent electrochemical performance and higher cost performance, but the working voltage is generally lower than 1.5V. The lithium ion battery has higher working voltage but high price, and because the organic solvent is used as the electrolyte, the battery has potential safety hazard in use. The invention aims to provide a method for manufacturing a high-voltage battery containing an aqueous electrolyte.
Disclosure of Invention
The principle of designing the high-voltage battery containing the aqueous electrolyte is that a proper diaphragm is adopted to enable the negative electrode reaction and the positive electrode reaction to occur in different environments, so that the negative electrode reaction has a lower reduction potential, the positive electrode reaction has a higher oxidation potential, and the battery has a higher working voltage. The negative electrode active material of the high-voltage battery containing the aqueous electrolyte is selected from materials with lower reduction potential, such as Zn, mg, al, fe, si, S, sulfite, phosphite, hypophosphite, borohydride and the like. The electrolyte used for the negative electrode is preferably an alkaline aqueous solution, such as a certain concentration of LiOH solution, naOH solution, KOH solution, ca (OH) 2 Solution, ammonia water, na 2 CO 3 Solutions, etc., or a mixture of several alkaline solutions. The high-voltage battery positive electrode active material containing aqueous electrolyte is selected from materials with higher oxidation potential, such as MnO 2 、PbO 2 Nickel oxide, cobalt oxide, hypobromite, hypochlorite, iodate, bromate, chlorate, potassium permanganate, ferrate, iodine, O 2 、H 2 O 2 And the like. The positive electrolyte is preferably an acidic aqueous solution, such as H with a certain concentration 2 SO 4 Solution, HCl solution, H 3 PO 4 Solution, HNO 3 Solutions, ammonium salt solutions, etc., or a mixture of several acidic solutions. The electrolyte used by one of the anode and the cathode can also be an organic solution, and the solvent can be DMSO, DMF, ethanol, acetonitrile and the like or a mixed solution of several organic solvents; the solute can be selected from LiOH, naOH, KOH, chloride, perchlorate, borate, acetate and the like, or a mixture of several salts. The supporting electrolyte used in the electrolytic solution may be sulfate, nitrate, chloride, ammonium salt, or the like. And a cation exchange membrane or an anion exchange membrane or a device capable of isolating the electrolyte and conducting ions is used as a diaphragm to isolate the electrolytes of the positive and negative electrodes.
The invention has the beneficial effects that: the cathode reaction and the anode reaction occur in different environments by adopting a proper diaphragm, so that the cathode reaction has a lower reduction potential, the anode reaction has a higher oxidation potential, and the battery has a higher working voltage. The used diaphragm can be recycled, and the battery has higher cost performance.
Detailed Description
Example 1
Negative electrode: zn;
and (3) cathode electrolyte: 4mol/LNaOH and 0.5mol/LNa 2 SO 4 Mixing the solution;
and (3) positive electrode: mnO 2 ︰superPLi︰PVDF=90︰5︰5；
The method for manufacturing the anode comprises the following steps: mixing manganese dioxide, conductive agent (super PLi) and binder (PVDF) according to a mass ratio of 90: 5, mixing with proper solvent, stirring uniformly, coating on a specific current collector, and drying;
anode electrolyte: 1mol/LH 2 SO 4 And 0.5mol/LNa 2 SO 4 Mixing the solution;
a diaphragm: nafion-Na + (sodium ion exchange membrane).
The battery is at 123.2mA/g MnO2 Discharging to 1.1V under current density, discharging medium voltage of 2.52V, and capacity of 500mAh/g MnO2 . The discharge curve is shown in figure 1.
Example 2
Negative electrode: zn;
and (3) cathode electrolyte: 8mol/L ammonia water and 0.5mol/LNa 2 SO 4 Mixing the solution;
and (3) positive electrode: mnO 2 ︰superPLi︰PVDF=90︰5︰5；
The method for manufacturing the anode comprises the following steps: mixing manganese dioxide, conductive agent (super PLi) and binder (PVDF) according to a mass ratio of 90: 5, mixing with proper solvent to obtain slurry, uniformly stirring, coating on a specific current collector, and drying;
positive electrodeElectrolyte solution: 1mol/LH 2 SO 4 And 0.5mol/LNa 2 SO 4 Mixing the solution;
a diaphragm: nafion-Na + (sodium ion exchange membrane).
The battery is at 246.4mA/g MnO2 Discharging to 1.1V under current density, discharging medium voltage of 2.32V, and capacity of 462mAh/g MnO2 . The discharge curve is shown in figure 2.
Example 3
Negative electrode: mg;
and (3) cathode electrolyte: saturated NH of V (DMSO): V (EtOH) = 1: 3 4 A Cl solution;
and (3) positive electrode: mnO 2 ︰superPLi︰PVDF=90︰5︰5；
The method for manufacturing the anode comprises the following steps: mixing manganese dioxide, conductive agent (super PLi) and binder (PVDF) according to a mass ratio of 90: 5, mixing with proper solvent to obtain slurry, uniformly stirring, coating on a specific current collector, and drying;
anode electrolyte: 1mol/LH 2 SO 4 And 0.5mol/LNa 2 SO 4 Mixed solution
Diaphragm: nafion-Na + (sodium ion exchange membrane).
The battery is at 60mA/g MnO2 The discharge curve at current density is shown in figure 3.
Example 4
Negative electrode: zn;
and (3) cathode electrolyte: 3mol/LNaOH and 0.5mol/LNa 2 SO 4 Mixing the solution;
and (3) positive electrode: carbon paper;
and (3) positive electrode electrolyte: 0.2mol/LKMno 4 、1mol/LH 2 SO 4 And 0.5mol/LNa 2 SO 4 Mixing the solution;
a diaphragm: nafion-Na + (sodium ion exchange membrane).
The battery is 200mA/cm 2 The discharge curve at current density is shown in figure 4.
Example 5
Negative electrode: zn;
and (3) cathode electrolyte: 3mol/LNaOH and 0.5mol/LNa 2 SO 4 Mixing the solution;
and (3) positive electrode: super PLi PVDF MnO 2 =75︰15︰5；
The method for manufacturing the anode comprises the following steps: mixing a conductive agent (SuperPLi), a binder (PVDF) and a catalyst (MnO) 2 ) Mixing at a mass ratio of 75: 15: 5, mixing with proper solvent, stirring, coating on a specific current collector, and drying;
anode electrolyte: mass fraction 5%H 2 O 2 、1mol/LH 2 SO 4 And 0.5mol/LNa 2 SO 4 Mixed solution
A diaphragm: nafion-Na + (sodium ion exchange membrane).
The battery is 200mA/cm 2 The discharge curve at current density is shown in figure 5.

Claims (9)

1. The high-voltage battery containing the aqueous electrolyte comprises a positive electrode, a negative electrode, a diaphragm, the positive electrolyte and the negative electrolyte, and is characterized in that: the positive electrode and the negative electrode of the battery are separated by a proper separator and are in different electrolytes, namely the electrochemical reaction of the positive electrode and the negative electrode occurs under different environments.
2. The high-voltage battery containing an aqueous electrolyte according to claim 1, characterized in that: the electrolyte of the positive electrode and the electrolyte of the negative electrode can be different aqueous solutions, or one electrode can be in the aqueous solution, and the other electrode is in the organic electrolyte.
3. The high-voltage battery comprising an aqueous electrolyte solution according to claim 1, wherein: the negative electrode is preferably alkaline electrolyte, such as LiOH solution, naO solutionH solution, KOH solution, ca (OH) 2 Solution, ammonia water, na 2 CO 3 Solutions, etc., or a mixture of several alkaline solutions.
4. The high-voltage battery containing an aqueous electrolyte according to claim 1, characterized in that: the positive electrode is preferably an acidic electrolyte, such as H with a certain concentration 2 SO 4 Solution, HCl solution, H 3 PO 4 Solution, HNO 3 Solutions, ammonium salt solutions, etc., or a mixture of several acidic solutions.
5. The high-voltage battery containing an aqueous electrolyte according to claim 1, characterized in that: when the organic solution is used as the electrolyte, the solvent can be DMSO, DMF, NMP, ethanol, acetonitrile and the like, or a mixed solution of several organic solvents; the solute can be selected from LiOH, naOH, KOH, chloride, perchlorate, borate, ammonium salt, acetate and the like, or a mixture of several salts.
6. The high-voltage battery containing an aqueous electrolyte according to claim 1, characterized in that: the diaphragm used in the battery is a cation exchange membrane or an anion exchange membrane or other devices capable of isolating the electrolyte and conducting ions.
7. The high-voltage battery comprising an aqueous electrolyte solution according to claim 1, wherein: the supporting electrolyte used in the electrolytic solution may be a sulfate, nitrate, chloride, ammonium salt, or the like.
8. The high-voltage battery containing an aqueous electrolyte according to claim 1, characterized in that: the negative active material is selected from materials with lower reduction potential, such as Zn, mg, al, fe, si, S, sulfite, phosphite, hypophosphite, borohydride and the like.
9. The high-voltage battery containing an aqueous electrolyte according to claim 1, characterized in that:the positive active material is selected from materials with higher oxidation potential, such as MnO 2 、PbO 2 Nickel oxide, cobalt oxide, hypobromite, hypochlorite, iodate, bromate, chlorate, potassium permanganate, ferrate, iodine, O 2 、H 2 O 2 And the like.
CN201510498772.7A 2015-08-14 2015-08-14 High voltage battery containing aqueous electrolyte Pending CN105140575A (en)

Priority Applications (1)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109309244A (en) * 2017-07-27 2019-02-05 南京工业大学 Hybrid water-based rechargeable battery
CN109979765A (en) * 2017-12-28 2019-07-05 南京理工大学 Method based on sodium sulfite electrolyte building Asymmetric Supercapacitor
CN110880621A (en) * 2019-01-31 2020-03-13 天津大学 High voltage rechargeable zinc-manganese battery
CN111200135A (en) * 2020-01-08 2020-05-26 李国钢 Acidic zinc-manganese primary battery and preparation method thereof
CN113363597A (en) * 2020-03-04 2021-09-07 中国科学院福建物质结构研究所 Aqueous ion battery
CN114039107A (en) * 2021-10-11 2022-02-11 瑞海泊有限公司 Manganese-zinc secondary battery of oil-water heterogeneous electrolyte system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102013536A (en) * 2010-10-28 2011-04-13 清华大学 Liquid flow type lithium-air battery
CN102341946A (en) * 2010-03-12 2012-02-01 住友电气工业株式会社 Redox flow battery
CN105009343A (en) * 2013-03-21 2015-10-28 日新电机株式会社 Electrical energy storage battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102341946A (en) * 2010-03-12 2012-02-01 住友电气工业株式会社 Redox flow battery
CN102013536A (en) * 2010-10-28 2011-04-13 清华大学 Liquid flow type lithium-air battery
CN105009343A (en) * 2013-03-21 2015-10-28 日新电机株式会社 Electrical energy storage battery

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109309244A (en) * 2017-07-27 2019-02-05 南京工业大学 Hybrid water-based rechargeable battery
CN109309244B (en) * 2017-07-27 2021-08-24 南京工业大学 Hybrid water-based rechargeable battery
CN109979765A (en) * 2017-12-28 2019-07-05 南京理工大学 Method based on sodium sulfite electrolyte building Asymmetric Supercapacitor
CN109979765B (en) * 2017-12-28 2021-10-26 南京理工大学 Method for constructing asymmetric super capacitor based on sodium sulfite electrolyte
CN110880621A (en) * 2019-01-31 2020-03-13 天津大学 High voltage rechargeable zinc-manganese battery
WO2020155190A1 (en) * 2019-01-31 2020-08-06 天津大学 High voltage rechargeable zinc-manganese battery
US11444335B2 (en) 2019-01-31 2022-09-13 Tianjin University High voltage rechargeable Zn—MnO2 battery
CN111200135A (en) * 2020-01-08 2020-05-26 李国钢 Acidic zinc-manganese primary battery and preparation method thereof
CN113363597A (en) * 2020-03-04 2021-09-07 中国科学院福建物质结构研究所 Aqueous ion battery
CN114039107A (en) * 2021-10-11 2022-02-11 瑞海泊有限公司 Manganese-zinc secondary battery of oil-water heterogeneous electrolyte system

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