CN114243110A - High-temperature-resistant bulging lithium-manganese dioxide soft package battery - Google Patents
High-temperature-resistant bulging lithium-manganese dioxide soft package battery Download PDFInfo
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- CN114243110A CN114243110A CN202111547787.XA CN202111547787A CN114243110A CN 114243110 A CN114243110 A CN 114243110A CN 202111547787 A CN202111547787 A CN 202111547787A CN 114243110 A CN114243110 A CN 114243110A
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- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 239000003792 electrolyte Substances 0.000 claims abstract description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 30
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 30
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 27
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 239000006230 acetylene black Substances 0.000 claims abstract description 18
- 239000002985 plastic film Substances 0.000 claims abstract description 15
- 229920006255 plastic film Polymers 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000006258 conductive agent Substances 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 31
- 229910052744 lithium Inorganic materials 0.000 claims description 31
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 20
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011267 electrode slurry Substances 0.000 description 30
- 238000007789 sealing Methods 0.000 description 27
- 210000004027 cell Anatomy 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 9
- 210000005056 cell body Anatomy 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008961 swelling Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 5
- 239000002000 Electrolyte additive Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006546 (C4-C10) cycloalkyl group Chemical group 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The invention belongs to the field of chemical batteries, and particularly relates to a high-temperature-swelling-resistant lithium-manganese dioxide soft package battery. The aluminum-plastic film electrolyte comprises an aluminum-plastic film shell with an opening at one end, wherein electrolyte is injected into the shell, lithium salt and an additive are dissolved in a mixed solvent to form the electrolyte, the additive is a mixture of 1, 3-propane sultone and phthalic anhydride, the content of the 1, 3-propane sultone is 0.8-2.7 wt% of the electrolyte, and the content of the phthalic anhydride is 0.2-1.8 wt% of the electrolyte; the positive plate comprises positive slurry, and comprises, by weight, 85-95% of electrolytic manganese dioxide, 2-7% of a composite conductive agent and 3-8% of a binder; the composite conductive agent consists of acetylene black, carbon nano tubes and water. The invention greatly reduces the gas generation of the battery at high temperature and optimizes the discharge performance of the battery, so that the lithium-manganese dioxide soft package battery has better high-temperature storage performance and discharge performance.
Description
Technical Field
The invention relates to the field of chemical batteries. And more particularly to a lithium-manganese dioxide soft package battery with high temperature swelling resistance.
Background
With the rapid development of portable electronic devices, lithium primary batteries (primary batteries using metal lithium or lithium alloy as a negative electrode material) are widely used in various fields such as industry, medicine, civil use, and military use due to their high specific energy, high specific power, and good storage properties. The lithium-manganese dioxide soft package battery is a battery with a positive electrode made of manganese dioxide and a shell packaged by an aluminum plastic packaging film, and is widely applied to portable electronic products. The conventional production steps of the lithium-manganese dioxide soft package battery sequentially comprise preparation of a naked battery core, shell installation of the naked battery core, top sealing, side sealing, testing, liquid injection, vacuum pre-sealing, pre-discharging and edge cutting. Because the shell of the lithium-manganese dioxide soft package battery adopts the aluminum plastic film, the shell is influenced by the use environment, seasons, climate and the like during actual use, so that the high temperature condition can be inevitably generated, gas is easily generated in the lithium-manganese dioxide soft package battery, the battery is expanded, the performance of the battery is attenuated, and even the battery is expanded and broken to cause potential safety hazards, so that the adaptability of the battery is limited.
Chinese patent application 202110293011.3 discloses an electrolyte additive for improving high-temperature gas expansion of a battery, which relates to the technical field of lithium ion batteries, wherein the additive comprises a1, 3-diphosphate-isothiazole compound and a water removal additive, and the general structural formula of the 1, 3-diphosphate-isothiazole compound is as follows: r1 and R2 are respectively and independently one selected from H, C1-8 alkyl, C4-10 cycloalkyl, C2-10 alkenyl, C2-10 alkynyl, C6-16 aryl, C6-16 heteroaryl and partial fluoro or perfluoro compounds thereof. The invention also provides an electrolyte and a lithium ion battery comprising the additive. In fact, the technology inhibits the reaction of the electrolyte and the anode and cathode materials in the lithium ion battery under the high-temperature condition by adding the special high-temperature flatulence improvement additive into the electrolyte, but the electrical property is reduced to some extent.
Disclosure of Invention
Aiming at the technical defects of the prior art, the invention aims to provide the lithium-manganese dioxide soft package battery electrolyte with high temperature swelling resistance, a mixture of 1, 3-propane sultone and phthalic anhydride is added into the electrolyte, and the electrolyte inhibits gas generation and has high thermal stability; meanwhile, the composite conductive agent in the positive electrode slurry is selected from acetylene black and carbon nano tubes, and the synergistic effect of the lithium salt of the electrolyte and the solvent is utilized, so that the discharge performance of the battery can be optimized while the gas generation of the battery at high temperature is reduced, and the lithium-manganese dioxide soft package battery has better high-temperature storage performance and discharge performance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a high-temperature-resistant bulging lithium-manganese dioxide soft package battery comprises an aluminum plastic film shell with an opening at one end, a lithium battery core arranged on the aluminum plastic film shell and a cover group embedded in the opening end of a shell; electrolyte is injected into the shell; the lithium battery core is formed by winding a positive plate, a negative plate and a diaphragm, the electrolyte is formed by dissolving lithium salt and an additive in a mixed solvent, the additive is a mixture of 1, 3-propane sultone and phthalic anhydride, the content of the 1, 3-propane sultone is 0.8-2.7 wt% of the electrolyte, and the content of the phthalic anhydride is 0.2-1.8 wt% of the electrolyte; the positive plate is prepared by rolling and embedding positive slurry and a positive current collector together through a roller press, drying through a drying furnace, rolling and cutting, wherein the positive slurry comprises, by weight, 85-95% of electrolytic manganese dioxide, 2-7% of a composite conductive agent and 3-8% of a binder; the composite conductive agent consists of acetylene black, carbon nano tubes and water, and the sum of the weight percentages of the components reaches 100 percent; the mass ratio of the acetylene black to the carbon nano tube is (3-6): (1-4).
Further: in the lithium-manganese dioxide soft package battery with high temperature swelling resistance, the lithium salt is at least one of lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6) and lithium tetrafluoroborate (LiBF4), and the content of the lithium perchlorate is 3-6 wt% of the electrolyte. A preferred lithium salt is lithium perchlorate (LiClO 4).
The content of the 1, 3-propane sultone is 1.3-2.3 wt% of the electrolyte, the content of phthalic anhydride is 0.4-1.3 wt% of the electrolyte, and the 1, 3-propane sultone is a negative electrode film forming additive, can be better than a solvent in reduction on a negative electrode, participates in forming an SEI film, improves the electrical property of the battery and prolongs the storage life of the battery. The additive for controlling the water content of the electrolyte by phthalic anhydride inevitably has trace moisture in the electrolyte, the moisture can damage the surface of an electrode material, and the moisture removal by phthalic anhydride can reduce the gas generation and the swelling of the battery caused by side reaction, thereby optimizing the discharge performance, the storage performance and the safety performance of the battery. The principle of the proportion adjustment of the two substances is based on the improvement of the storage performance and the safety performance of the battery under the condition of improving the discharge performance of the battery.
The solvent is at least one of 1, 3-dioxolane, propylene carbonate, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. The preferred solvent is at least one of 1, 3-dioxolane, propylene carbonate and ethylene glycol dimethyl ether. The preferable solvent is a mixture of propylene carbonate and ethylene glycol dimethyl ether, the content of the propylene carbonate is 45-65 wt% of the electrolyte, the content of the ethylene glycol dimethyl ether is 30-50 wt% of the electrolyte, the preferable content of the propylene carbonate is 50-60 wt% of the electrolyte, and the content of the ethylene glycol dimethyl ether is 35-45 wt% of the electrolyte. The propylene carbonate has high dielectric constant, chemical stability and electrochemical stability, and high thermal stability can enable the battery to have good high-temperature performance including high-temperature discharge and high-temperature storage. Ethylene glycol dimethyl ether: the battery has the advantages of low viscosity, high conductivity, low flash point, good low-temperature performance and good discharge performance, and can improve the low-temperature high-rate discharge performance of the battery on the premise of ensuring the high performance at room temperature and the high-temperature safety.
And further: in the lithium-manganese dioxide soft package battery with high temperature swelling resistance, the mass ratio of acetylene black to carbon nano tubes is (3-4): (2-3). The conductivity of the positive electrode is improved by optimizing the conductive agent and adding a proper amount of carbon nanotubes with good conductive effect, so that the discharge capacity of the lithium primary battery is improved; compared with the common conductive agent, the carbon nano tube has higher cost, and the addition of the carbon nano tube is controlled while the discharge capacity of the battery is improved, so that the increase of the cost of the battery is reduced.
The binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber and LA133/LA 135. LA133/LA135 is two different types of binders for aqueous dispersions of acrylonitrile multipolymer compounds.
Compared with the prior art, the high-temperature-swelling-resistant lithium manganese dioxide soft package battery has the advantages that the additive of the electrolyte is a mixture of 1, 3-propane sultone and phthalic anhydride, the content of the 1, 3-propane sultone is 0.8-2.7 wt% of the electrolyte, and the content of the phthalic anhydride is 0.2-1.8 wt% of the electrolyte; the positive plate is prepared by rolling and embedding positive slurry and a positive current collector together through a roller press, drying through a drying furnace, rolling and cutting, wherein the positive slurry comprises, by weight, 85-95% of electrolytic manganese dioxide, 2-7% of a composite conductive agent and 3-8% of a binder; the composite conductive agent consists of acetylene black, carbon nano tubes and water; the mass ratio of the acetylene black to the carbon nano tube is (3-6): (1-4). 1, 3-propane sultone ester and anhydride compound of phthalic anhydride are added into the electrolyte, and through inhibiting gas generation and high thermal stability performance and utilizing the synergistic effect between electrolyte lithium salt and solvent, the discharge performance of the battery can be optimized while gas generation caused by the battery at high temperature is reduced, so that the lithium-manganese dioxide soft package battery has excellent high-temperature storage performance and discharge performance.
Detailed Description
The main point of the invention is that the mixture of 3-propane sultone and phthalic anhydride is used as an additive, and the composite conductive agent consisting of acetylene black, carbon nano tubes and water is selected, so that the discharge performance of the battery is optimized while the gas generated by the battery at high temperature is greatly reduced, and the lithium-manganese dioxide soft package battery has better high-temperature storage performance and discharge performance. The present invention will be further described with reference to the following examples, which are not intended to limit the present invention, and the selection of the raw materials can be made according to the circumstances without substantially affecting the results.
Example 1
The lithium-manganese dioxide soft package battery with high temperature swelling resistance is manufactured to evaluate the swelling performance of the battery under the high temperature condition and the discharge performance of the battery under various discharge systems.
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 50 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 43 wt% of the electrolyte, the content of 1, 3-propane sultone is 1.3 wt% of the electrolyte, and the content of phthalic anhydride is 0.7 wt% of the electrolyte.
Preparing a positive plate: the method comprises the steps of rolling and embedding positive electrode slurry and a positive electrode current collector together through a roller press, drying the positive electrode slurry in a drying furnace at 200 ℃, rolling and cutting the positive electrode slurry to obtain the slurry, wherein the positive electrode slurry comprises the following components in percentage by weight, and is prepared by fully mixing 91% of MnO2, 4% of acetylene black, 1% of carbon nano tubes and deionized water, and fully mixing the mixture with 4% of polytetrafluoroethylene.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Example 2
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 50 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 43 wt% of the electrolyte, the content of 1, 3-propane sultone is 1.8 wt% of the electrolyte, and the content of phthalic anhydride is 0.2 wt% of the electrolyte.
Preparing a positive plate: the method comprises the steps of rolling and embedding positive electrode slurry and a positive electrode current collector together through a roller press, drying the positive electrode slurry in a drying furnace at 190 ℃, rolling and cutting the positive electrode slurry to obtain the cathode material, wherein the positive electrode slurry comprises the following components in percentage by weight, 89.5% of MnO2, 3% of acetylene black, 2% of carbon nano tubes and deionized water are fully mixed, and then the cathode material and 5.5% of polytetrafluoroethylene are fully mixed to obtain the slurry.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Example 3
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 55 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 38 wt% of the electrolyte, the content of 1, 3-propane sultone is 1.5 wt% of the electrolyte, and the content of phthalic anhydride is 0.5 wt% of the electrolyte.
Preparing a positive plate: the positive electrode slurry and a positive electrode current collector are rolled and embedded together through a roller press, dried through a drying furnace drying oven at 200 ℃, rolled and cut to obtain the positive electrode slurry, and the positive electrode slurry comprises the following components, by weight, 92% of MnO2, 4% of acetylene black, 2.5% of carbon nano tubes and deionized water, and is fully mixed with 1.5% of LA133 to obtain the slurry.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Example 4
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 55 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 37.7 wt% of the electrolyte, the content of 1, 3-propane sultone is 1.5 wt% of the electrolyte, and the content of phthalic anhydride is 0.8 wt% of the electrolyte.
Preparing a positive plate: the positive electrode slurry and a positive electrode current collector are rolled and embedded together through a roller press, dried through a drying furnace drying oven at 190 ℃, rolled and cut to obtain the positive electrode slurry, and the positive electrode slurry comprises the following components, by weight, 90% of MnO2, 6% of acetylene black, 3% of carbon nanotubes and deionized water, and is fully mixed with 1% of LA133 to obtain the slurry.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Example 5
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 55 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 37.5 wt% of the electrolyte, the content of 1, 3-propane sultone is 1.5 wt% of the electrolyte, and the content of phthalic anhydride is 1 wt% of the electrolyte.
Preparing a positive plate: the method comprises the steps of rolling and embedding positive electrode slurry and a positive electrode current collector together through a roller press, drying the positive electrode slurry and the positive electrode current collector in a drying furnace at 180 ℃, rolling and cutting the positive electrode slurry to obtain the positive electrode slurry, wherein the positive electrode slurry comprises the following components, by weight, 87% of MnO2, 5% of acetylene black, 2% of carbon nano tubes and deionized water, and is fully mixed with 6% of polytetrafluoroethylene to obtain the slurry.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Example 6
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 53 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 39 wt% of the electrolyte, the content of 1, 3-propane sultone is 2 wt% of the electrolyte, and the content of phthalic anhydride is 1 wt% of the electrolyte.
Preparing a positive plate: the method comprises the steps of rolling and embedding positive electrode slurry and a positive electrode current collector together through a roller press, drying the positive electrode slurry in a drying furnace at 200 ℃, rolling and cutting the positive electrode slurry to obtain the anode material, wherein the positive electrode slurry comprises, by weight, 89% of MnO2, 4% of acetylene black, 3% of carbon nano tubes and deionized water, and is fully mixed with 4% of polytetrafluoroethylene to obtain the anode material.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Comparative example 1
Preparing an electrolyte: dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 55 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 38 wt% of the electrolyte, and the content of 1, 3-propane sultone is 2 wt% of the electrolyte.
Preparing a positive plate: the positive electrode slurry and a positive electrode current collector are rolled and embedded together through a roller press, dried through a drying furnace drying oven at 200 ℃, rolled and cut to obtain the positive electrode slurry, and the positive electrode slurry comprises the following components, by weight, 89% of MnO2, 3% of acetylene black, 2% of graphite and deionized water, and is fully mixed with 6% of polytetrafluoroethylene to obtain the slurry.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Comparative example 2
Preparing an electrolyte: and dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 55 w% of the electrolyte, the content of ethylene glycol dimethyl ether is 38.7 wt% of the electrolyte, and the content of phthalic anhydride is 1.3 wt% of the electrolyte.
Preparing a positive plate: the positive electrode slurry and a positive electrode current collector are rolled and embedded together through a roller press, dried in a drying oven at 200 ℃, rolled and cut to obtain the positive electrode slurry, and the positive electrode slurry comprises the following components, by weight, 89% of MnO2, 5% of carbon fibers and deionized water, and is fully mixed with 6% of polytetrafluoroethylene to obtain the slurry.
Preparing a lithium-manganese dioxide soft package battery: and adding a diaphragm between the prepared positive plate and the lithium strip negative plate, winding the positive plate and the lithium strip negative plate in a square mode to form a bare cell, then placing the bare cell into a formed aluminum-plastic film shell, performing top sealing, side sealing and testing to obtain a packaged lithium cell body, then injecting the prepared electrolyte and performing vacuum pre-sealing, performing pre-discharging, and then cutting edges to form the CF302752 type lithium-manganese dioxide soft package battery.
Comparative example 3
Preparing an electrolyte: and dissolving lithium perchlorate and an additive in a mixed solvent, wherein the content of the lithium perchlorate is 5 wt% of the electrolyte, the content of propylene carbonate is 55 w% of the electrolyte, and the content of ethylene glycol dimethyl ether is 40 wt% of the electrolyte.
A positive plate and a lithium-manganese dioxide pouch cell were prepared as described in comparative example 1.
Comparative examples 1, 2, 3 differ from examples 1-6 in that: comparative example 1 did not use phthalic anhydride, comparative example 2 did not use 1, 3-propane sultone, and comparative example 3 did not use phthalic anhydride and 1, 3-propane sultone.
Comparative examples 1, 2, and 3 in comparison with examples 1 to 6, the composite conductive agent of the positive electrode paste further includes carbon nanotubes.
The batteries prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to a pulse discharge test, a high-temperature storage test and a safety performance test, and the test results are shown in tables 1, 2 and 3:
table 1: comparison of normal-temperature pulse discharge capacity of CF302752 type lithium-manganese dioxide soft-package battery
Table 2: comparison of 60 ℃ storage performance of CF302752 type lithium-manganese dioxide soft-package battery
Table 3: comparison of safety performance of CF302752 type lithium-manganese dioxide soft-packed battery
By comparing the discharge performance of examples 1 to 6 and comparative examples 1 to 3 in table 1, it is found that the discharge performance of the lithium-manganese dioxide pouch battery using no phthalic anhydride and no 1, 3-propane sultone in the electrolyte is very poor, indicating that the use of phthalic anhydride and no 1, 3-propane sultone as the electrolyte additive can effectively improve the discharge performance of the lithium-manganese dioxide pouch battery.
Through comparison of discharge performance of examples 1 to 6 and comparative examples 1 to 3 in table 2, it is found that the high-temperature storage performance of the lithium-manganese dioxide soft pack battery using no phthalic anhydride and no 1, 3-propane sultone in the electrolyte is very poor, indicating that the high-temperature storage performance of the lithium-manganese dioxide soft pack battery can be effectively improved by using phthalic anhydride and no 1, 3-propane sultone as the electrolyte additives.
By comparing the discharge performance of examples 1 to 6 and comparative examples 1 to 3 in table 1, it is found that the safety performance of the lithium-manganese dioxide pouch battery using no phthalic anhydride and no 1, 3-propane sultone in the electrolyte is very poor, indicating that the safety performance of the lithium-manganese dioxide pouch battery can be effectively improved by using phthalic anhydride and no 1, 3-propane sultone as the electrolyte additive.
The foregoing is only a preferred embodiment of this invention and any obvious combination of alternatives, modifications and variations thereof are within the scope of the invention without departing from the spirit of the invention. It should be understood that the examples are merely for illustrative purposes and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A high-temperature-resistant bulging lithium-manganese dioxide soft package battery comprises an aluminum plastic film shell with an opening at one end, a lithium battery core arranged on the aluminum plastic film shell and a cover group embedded in the opening end of a shell; electrolyte is injected into the shell; the lithium battery core is formed by winding a positive plate, a negative plate and a diaphragm, and is characterized in that:
the electrolyte is formed by dissolving lithium salt and an additive in a mixed solvent, wherein the additive is a mixture of 1, 3-propane sultone and phthalic anhydride, the content of the 1, 3-propane sultone is 0.8-2.7 wt% of the electrolyte, and the content of the phthalic anhydride is 0.2-1.8 wt% of the electrolyte;
the positive plate is prepared by rolling and embedding positive slurry and a positive current collector together through a roller press, drying through a drying furnace, rolling and cutting, wherein the positive slurry comprises, by weight, 85-95% of electrolytic manganese dioxide, 2-7% of a composite conductive agent and 3-8% of a binder, and the sum of the weight percentages of the components reaches 100%; the composite conductive agent consists of acetylene black, carbon nano tubes and water; the mass ratio of the acetylene black to the carbon nano tube is (3-6): (1-4).
2. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 1, wherein: the lithium salt is at least one of lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6) and lithium tetrafluoroborate (LiBF4), and the content of the lithium perchlorate is 3-6 wt% of the electrolyte.
3. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 2, wherein: the lithium salt is lithium perchlorate (LiClO 4).
4. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 1, wherein: the content of the 1, 3-propane sultone is 1.3-2.3 wt% of the electrolyte, and the content of the phthalic anhydride is 0.4-1.3 wt% of the electrolyte.
5. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 1, wherein: the solvent is at least one of 1, 3-dioxolane, propylene carbonate, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.
6. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 5, wherein: the solvent is at least one of 1, 3-dioxolane, propylene carbonate and ethylene glycol dimethyl ether.
7. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 6, wherein: the solvent is a mixture of propylene carbonate and ethylene glycol dimethyl ether, the content of the propylene carbonate is 45-65 wt% of the electrolyte, and the content of the ethylene glycol dimethyl ether is 30-50 wt% of the electrolyte.
8. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 7, wherein: the content of the propylene carbonate is 50-60 wt% of the electrolyte, and the content of the ethylene glycol dimethyl ether is 35-45 wt% of the electrolyte.
9. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 1, wherein: the mass ratio of the acetylene black to the carbon nano tube is (3-4): (2-3).
10. The lithium-manganese dioxide pouch cell resistant to high temperature ballooning of claim 1, wherein: the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber and LA133/LA 135.
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