CN116632249B - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN116632249B CN116632249B CN202310925719.5A CN202310925719A CN116632249B CN 116632249 B CN116632249 B CN 116632249B CN 202310925719 A CN202310925719 A CN 202310925719A CN 116632249 B CN116632249 B CN 116632249B
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- electrode active
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 claims abstract description 37
- 239000007773 negative electrode material Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 239000010439 graphite Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000006183 anode active material Substances 0.000 claims description 9
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 17
- 239000011149 active material Substances 0.000 abstract description 16
- 238000004804 winding Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 39
- 239000011230 binding agent Substances 0.000 description 35
- 229910003002 lithium salt Inorganic materials 0.000 description 30
- 159000000002 lithium salts Chemical class 0.000 description 30
- 238000002156 mixing Methods 0.000 description 30
- 239000011267 electrode slurry Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- 239000002904 solvent Substances 0.000 description 24
- 229910013870 LiPF 6 Inorganic materials 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 239000004014 plasticizer Substances 0.000 description 21
- 239000004698 Polyethylene Substances 0.000 description 20
- 230000009471 action Effects 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 20
- -1 polyethylene Polymers 0.000 description 20
- 229920000573 polyethylene Polymers 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 239000006230 acetylene black Substances 0.000 description 19
- 239000006258 conductive agent Substances 0.000 description 19
- 239000006256 anode slurry Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000002174 Styrene-butadiene Substances 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 239000011888 foil Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000002955 isolation Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 238000007493 shaping process Methods 0.000 description 10
- 239000002562 thickening agent Substances 0.000 description 10
- 238000009461 vacuum packaging Methods 0.000 description 10
- 229910013872 LiPF Inorganic materials 0.000 description 9
- 101150058243 Lipf gene Proteins 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000003090 exacerbative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
- 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
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery, which comprises: the positive plate comprises a positive current collector and a positive active material layer arranged on the surface of the positive current collector, and the negative plate comprises a negative current collector and a negative active material layer arranged on the surface of the negative current collector; the positive electrode active material layer and the negative electrode active material layer both comprise propylene carbonate, and the content Cc of propylene carbonate in the positive electrode active material layer per unit mass and the content Ca of propylene carbonate in the negative electrode active material layer per unit mass are both greater than 0mg/g, and the content Cc of propylene carbonate in the positive electrode active material layer per unit mass is smaller than the content Ca of propylene carbonate in the negative electrode active material layer per unit mass. The lithium ion battery can solve the problems that the active material layer is cracked in the drying process of the positive and negative electrode plates and the active material layer is fallen off in the winding process of the battery core, so that the cycle life of the lithium ion battery is prolonged.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, high power density, good safety performance, quick charge and discharge, long cycle life, no pollution, no memory effect and the like, and is widely applied to the fields of portable equipment, aerospace, urban rail transit and the like. With the gradual development of lithium ion battery technology and the continuous advancement of new energy industries in China, the requirement of the automobile industry on high energy density of lithium ion batteries is gradually increased in recent years. At present, in order to obtain a lithium ion battery with high energy density, a method is often adopted to increase the loading capacity of active substances in unit area on positive and negative current collectors of the lithium ion battery, namely to increase the surface density of positive and negative pole pieces of the lithium ion battery. However, when the surface density of the positive and negative electrode plates is high, the active material layers of the positive and negative electrode plates all contain high-molecular rigid long-chain structural binders, so that the glass transition temperature is high, the long-chain molecular movement capacity is poor, the rigidity is high, the active material layers on the positive and negative electrode plates are easy to crack in the process of coating and drying, the flexibility of the positive and negative electrode plates is poor, the active material layers on the positive and negative electrode plates are easy to fall off in the process of winding the battery core, and the cycle life of the lithium ion battery is reduced.
Disclosure of Invention
In order to solve the above-mentioned defect in the prior art, the present invention aims to provide a lithium ion battery, which can solve the problems of cracking of an active material layer in the drying process of positive and negative electrode plates and falling of the active material layer in the winding process of a battery core, so as to improve the cycle life of the lithium ion battery.
The technical scheme provided by the invention is as follows:
a lithium ion battery, comprising: the positive plate comprises a positive current collector and a positive active material layer arranged on the surface of the positive current collector, and the negative plate comprises a negative current collector and a negative active material layer arranged on the surface of the negative current collector;
the positive electrode active material layer and the negative electrode active material layer both comprise propylene carbonate, and the content Cc of propylene carbonate in the positive electrode active material layer per unit mass and the content Ca of propylene carbonate in the negative electrode active material layer per unit mass are both greater than 0mg/g, and the content Cc of propylene carbonate in the positive electrode active material layer per unit mass is smaller than the content Ca of propylene carbonate in the negative electrode active material layer per unit mass.
According to the invention, the plasticizer Propylene Carbonate (PC) is added into the positive and negative active material layers, and the PC has a small molecular structure, so that the PC can enter between molecular chains of a high molecular binder, the interaction force between the molecular chains is reduced, a certain plasticizing effect is achieved on a high molecular rigid long chain of the binder, the glass transition temperature of the high molecular binder is reduced, the flexibility of the binder and the positive and negative active material layers is improved, thereby avoiding cracking of the active material layers in the drying process of the positive and negative electrode plates, and simultaneously avoiding the problem that the active material layers fall off due to poor flexibility of the positive and negative electrode plates in the winding process.
In addition, the invention discovers that PC is added in the positive and negative active material layers, and the PC swells into the inside of the binder molecules of the active material layers to guide the binder to pre-swell, so that the binder can better absorb electrolyte solvents in the stage of injecting the lithium ion battery into the electrolyte. Therefore, a certain amount of PC is absorbed in advance by the binder, so that the eutectic point of an electrolyte solvent system can be reduced, the electrolyte is more uniformly distributed in the anode and the cathode, the current density is more uniform, and a solid electrolyte film formed on the surfaces of the anode and the cathode active material layers is more uniform and compact in the formation process of the lithium ion battery.
In addition, when the positive electrode active material in the positive electrode active material layer is a 6-series or more nickel-cobalt-manganese ternary material, lattice oxygen loss of the positive electrode active material is more likely to occur due to the corrosion of the positive electrode active material by the electrolyte. The invention can help the surface of the positive electrode active material layer to form a uniform and compact solid electrolyte membrane by pre-swelling the PC in the binder in the positive electrode active material layer, so as to better protect the positive electrode interface, prevent the corrosion of electrolyte and further prolong the cycle life of the lithium ion battery.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
In the present invention, LFP is LiFePO 4 PVDF is polyvinylidene fluoride, PC is propylene carbonate, NMP is N-methyl pyrrolidone, CMC is sodium carboxymethyl cellulose, SBR is styrene butadiene rubber, EC is ethylene carbonate, EMC is methyl ethyl carbonate, DEC is diethyl carbonate.
In the present invention, cc represents the content of propylene carbonate in the positive electrode active material layer per unit mass, and Ca represents the content of propylene carbonate in the negative electrode active material layer per unit mass.
Example 1
1) Preparation of positive plate
The positive electrode active material LFP, the conductive agent acetylene black, the binder PVDF and the plasticizer PC are mixed according to the mass ratio of 96.45:1Mixing 5:2:0.05, adding NMP solvent into the mixture, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the double-sided density to be 330g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active material graphite, conductive agent acetylene black, thickener CMC, binder SBR and plasticizer PC according to the mass ratio of 96.4:1:1:1.4:0.2, adding solvent deionized water into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform, thus obtaining negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 150g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the embodiment.
Example 2
1) Preparation of positive plate
Mixing an anode active material LFP, a conductive agent acetylene black, a binder PVDF and a plasticizer PC according to a mass ratio of 96:1.5:2:0.5, adding a solvent NMP into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite aluminum foils of a positive electrode current collectorSurface and controlling the double-sided density to 447g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing a negative electrode active material graphite, a conductive agent acetylene black, a thickener CMC, a binder SBR and a plasticizer PC according to a mass ratio of 94.6:1:1:1.4:2, adding deionized water serving as a solvent into the mixed material, and stirring under the action of a vacuum stirrer until the system is uniform to obtain a negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 200g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the embodiment.
Example 3
1) Preparation of positive plate
Mixing an anode active material LFP, a conductive agent acetylene black, a binder PVDF and a plasticizer PC according to a mass ratio of 95.5:1.5:2:1, adding a solvent NMP into the mixture formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the double-sided density to be 555g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Negative electrode active materialMixing graphite, a conductive agent acetylene black, a thickener CMC, a binder SBR and a plasticizer PC according to a mass ratio of 92.6:1:1:1.4:4, adding a solvent deionized water into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain a negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 260g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the embodiment.
Example 4
1) Preparation of positive plate
The positive electrode active material LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NCM 622), a conductive agent acetylene black, a binder PVDF and a plasticizer PC are mixed according to a mass ratio of 96:1.5:2:0.5, then a solvent NMP is added into the mixed material formed by the mixing, and the mixed material is stirred under the action of a vacuum stirrer until the system is uniform, so that positive electrode slurry is obtained; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the density of the two surfaces to 267g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active material graphite, conductive agent acetylene black, thickener CMC, binder SBR and plasticizer PC according to the mass ratio of 94.6:1:1:1.4:2, and then adding into the mixture formed by the materialsSolvent deionized water is stirred under the action of a vacuum stirrer until the system is uniform, and negative electrode slurry is obtained; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 150g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the embodiment.
Example 5
1) Preparation of positive plate
Mixing an anode active material NCM622, a conductive agent acetylene black, a binder PVDF and a plasticizer PC according to a mass ratio of 96:1.5:2:0.5, adding a solvent NMP into the mixture, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the density of the two surfaces to be 320g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active materials graphite, silica, a conductive agent acetylene black, a thickening agent CMC, a binder SBR and a plasticizer PC according to a mass ratio of 91.6:3:1:1:1.4:2, adding solvent deionized water into the mixed materials formed by the mixing materials, and stirring under the action of a vacuum stirrer until the system is uniform to obtain negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 185g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the embodiment.
Example 6
1) Preparation of positive plate
Mixing an anode active material NCM622, a conductive agent acetylene black, a binder PVDF and a plasticizer PC according to a mass ratio of 96:1.5:2:0.5, adding a solvent NMP into the mixture, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the density of the two surfaces to be 310g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active material graphite, silicon carbon, conductive agent acetylene black, thickener CMC, binder SBR and plasticizer PC according to the mass ratio of 91.6:3:1:1:1.4:2, adding solvent deionized water into the mixture, and stirring under the action of a vacuum stirrer until the system is uniform to obtain negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 180g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then the organic solvent is addedAdding fully dried lithium salt LiPF 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the embodiment.
Comparative example 1
1) Preparation of positive plate
Mixing an anode active material NCM622, a conductive agent acetylene black and a binder PVDF according to a mass ratio of 96.5:1.5:2, adding a solvent NMP into the mixture formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the double-sided density to be 506g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active material graphite, conductive agent acetylene black, thickener CMC and binder SBR according to a mass ratio of 96.6:1:1:1.4, adding solvent deionized water into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the double-sided density to be 250g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the comparative example.
Comparative example 2
1) Preparation of positive plate
Mixing an anode active material NCM622, a conductive agent acetylene black and a binder PVDF according to a mass ratio of 96.5:1.5:2, adding a solvent NMP into the mixture formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the double-sided density to be 516g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing a negative electrode active material graphite, a conductive agent acetylene black, a thickener CMC, a binder SBR and a plasticizer PC according to a mass ratio of 94.6:1:1:1.4:2, adding deionized water serving as a solvent into the mixed material, and stirring under the action of a vacuum stirrer until the system is uniform to obtain a negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 280g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the comparative example.
Comparative example 3
1) Preparation of positive plate
Positive electrode active material NCM622, conductive agent acetylene black, binder PVDF and plasticizer PC are mixed according to the mass ratio of 96:1.5:2:0.5, mixing, adding a solvent NMP into the mixture formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain positive electrode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the double-sided density to be 504g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active material graphite, conductive agent acetylene black, thickener CMC and binder SBR according to a mass ratio of 96.6:1:1:1.4, adding solvent deionized water into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the density of the two surfaces to be 280g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the comparative example.
Comparative example 4
1) Preparation of positive plate
Acetylene as positive electrode active material LFP and conductive agentBlack, binder PVDF and plasticizer PC according to the mass ratio of 94.5:1.5:2:2, mixing, adding a solvent NMP into the mixture formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain positive electrode slurry; uniformly coating the positive electrode slurry on two opposite surfaces of a positive electrode current collector aluminum foil, and controlling the double-sided density to be 560g/m 2 And (5) carrying out cold pressing and cutting after drying by a baking oven to obtain the positive plate.
2) Preparation of negative plate
Mixing negative electrode active material graphite, conductive agent acetylene black, thickener CMC, binder SBR and plasticizer PC according to the mass ratio of 96.4:1:1:1.4:0.2, adding solvent deionized water into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform, thus obtaining negative electrode slurry; uniformly coating the anode slurry on two opposite surfaces of an anode current collector copper foil, and controlling the double-sided density to be 250g/m 2 And (5) rolling and slitting after drying by an oven to obtain the negative plate.
3) Preparing an electrolyte: EC, EMC, DEC is mixed according to the volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried lithium salt LiPF is added into the organic solvent 6 Stirring to lithium salt LiPF 6 Completely dissolve to prepare and obtain lithium salt LiPF 6 An electrolyte with a concentration of 1 mol/L.
4) And (3) battery assembly: sequentially stacking the positive plate, the polyethylene diaphragm and the negative plate in the step 1) and the step 2), enabling the polyethylene diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery of the comparative example.
Table 1 shows the parameter characteristics of the positive and negative plates of examples 1-6 and comparative examples 1-4.
TABLE 1
Performance testing and analysis
1. Test object: positive electrode sheets, negative electrode sheets, and lithium ion batteries prepared in examples 1 to 6 and comparative examples 1 to 4.
2. Test item
1) PC content in positive and negative plates
Drying and shearing the positive plate and the negative plate prepared in the same batch in the examples 1-6 and the comparative examples 1-4, using methanol solvent for ultrasonic treatment for 2min, respectively extracting the plasticizer PC in the positive plate and the negative plate, filtering by using a nylon membrane, and respectively carrying out quantitative test by using a gas chromatograph to obtain the PC content in the positive plate and the negative plate.
2) Cycle performance test
When LFP is used as an anode active material, constant-current and constant-voltage charging is carried out to 3.65V at 60 ℃ by using 1C current, the battery is kept stand for 10min, then constant-current discharging is carried out to 2.5V by using 1C current, the battery is kept stand for 10min, and the battery is circulated until 600 circles of lithium ion batteries are circulated, and the battery capacity retention rate at the moment is calculated. Capacity retention = battery capacity/initial battery capacity after 600 cycles 100%.
When NCM622 is used as a positive electrode active material, constant-current and constant-voltage charging is carried out at 60 ℃ with a current of 1C to 4.35V, standing is carried out for 10min, then constant-current discharging is carried out with a current of 1C to 2.75V, standing is carried out for 10min, circulation is carried out until the lithium ion battery circulates for 600 circles, and the battery capacity retention rate at the moment is calculated. Capacity retention = battery capacity/initial battery capacity after 600 cycles 100%.
3) Cracking condition of positive and negative plates
The positive electrode slurries and the negative electrode slurries prepared in the same batch of examples 1 to 6 and comparative examples 1 to 4 were uniformly coated on the opposite surfaces of the positive electrode current collector aluminum foil and the negative electrode current collector copper foil at a speed of 2m/min for 6m, respectively, dried in an oven at 100 ℃, and the cracking condition of the active material layers of the positive and negative electrode sheets was observed.
3. Test results: see table 2.
TABLE 2
Referring to table 2, comparing the test results of examples 1-6 and comparative examples 1-3, it is known that the addition of the plasticizer PC to the positive and negative electrode slurries can exert a certain plasticizing effect on the high molecular rigid long chain of the binder, reduce the glass transition temperature of the binder, and improve the flexibility of the binder and the positive and negative electrode active material layers, thereby avoiding cracking of the active material layers during drying of the positive and negative electrode sheets, and further weakening the falling of the active material layers during winding of the battery core, and further prolonging the cycle life of the lithium ion battery, so that the capacity retention rate of the lithium ion battery is more than 87% and even up to 94.5% after 600 charge and discharge cycles at 60 ℃.
Comparing the test results of examples 1-6 with comparative example 4 shows that the PC content in the negative electrode sheet is higher than that in the positive electrode sheet, which is more beneficial to improving the cycle performance of the lithium ion battery. On the one hand, NMP is used as a solvent in the positive electrode slurry, water is used as a solvent in the negative electrode slurry, the polarity of NMP is higher than that of water, and the plasticizing effect on the high-molecular rigid long-chain binder is better, so that the content of the plasticizer required by the positive electrode is lower than that of the negative electrode; on the other hand, the addition of the plasticizer is favorable for the swelling of the binder, so that the absorption of the electrolyte is promoted, and because the SEI film formed on the surface of the negative electrode active material layer is favorable for the long-term circulation of the lithium ion battery, the improvement of the PC content in the negative electrode sheet is favorable for enhancing the liquid retaining capacity of the negative electrode active material layer, so that the repair of the SEI film is favorable, and the circulation performance of the lithium ion battery is further improved.
Referring to the data of examples 1 to 3 in tables 1 and 2, the capacity retention rates of the lithium ion batteries of examples 1 to 3 after 600 cycles of charge and discharge were increased and then decreased. The main difference between examples 1 to 3 is that the amount of positive and negative electrode PC added and the double-sided density of the positive and negative electrode sheets are sequentially increased from example 1 to example 3. From the above analysis, it is known that the addition of PC can avoid cracking of the active material layer during drying of the positive and negative electrode plates, and further weaken the falling of the active material layer during winding of the battery core, thereby prolonging the cycle life of the lithium ion battery. But is provided withIn example 3, the density of both surfaces of the positive and negative electrode sheets is too high, so that the internal resistance of the lithium ion battery is increased, and the cycle performance of the lithium ion battery in example 3 is reduced. The positive and negative plates of example 2 had a higher double-sided density than that of example 1, but did not lower the cycle performance of the lithium ion battery, indicating that the double-sided density was not higher than 447g/m 2 The double-sided density of the negative plate is not higher than 200g/m 2 On the basis of the above, the internal resistance of the battery is less in change, and the cycle performance of the lithium ion battery cannot be influenced.
Referring to the data of examples 4 to 6 in tables 1 and 2, according to the above analysis, the effect of the double-sided density of the positive and negative electrode sheets of examples 4 to 6 on the internal resistance of the lithium ion battery was small, that is, the effect on the cycle performance of the lithium ion battery was small, and on this basis, examples 4 to 6 were mainly different in that the negative electrode active material, graphite, was used as the negative electrode active material of example 4, the capacity retention rate of the corresponding lithium ion battery was 94.5%, graphite+3wt% silicon, the capacity retention rate of the corresponding lithium ion battery was 92.3%, and graphite+3wt% silicon carbon was used as the negative electrode active material of example 6, which indicated that the addition of silicon and silicon carbon reduced the cycle performance of the lithium ion battery. This is because the volume expansion of the silicon oxygen material and the silicon carbon material during the charge and discharge cycle of the lithium ion battery is more severe than that of the graphite material, and the active material itself is more likely to be broken to generate more new interfaces, thereby exacerbating the side reaction of the electrolyte, exacerbating the consumption of active lithium, and thus reducing the cycle life of the lithium ion battery.
In the lithium ion battery of the above embodiment, when lithium nickel cobalt manganate is used as the ternary positive electrode material, NCM622 is used as an example, and NCM712, NCM811, NCM955, etc. may be selected as the ternary positive electrode material in actual production, but as the nickel content increases, the positive electrode active material is corroded more severely by the electrolyte, lattice oxygen loss is more likely to occur, so that the cycle life of the lithium ion battery of NCM622 is optimal under the same manufacturing process conditions and the same test conditions.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (11)
1. A lithium ion battery, comprising: the positive plate comprises a positive current collector and a positive active material layer arranged on the surface of the positive current collector, and the negative plate comprises a negative current collector and a negative active material layer arranged on the surface of the negative current collector;
the positive electrode active material layer and the negative electrode active material layer each include propylene carbonate, and the content Cc of propylene carbonate in the positive electrode active material layer per unit mass and the content Ca of propylene carbonate in the negative electrode active material layer are both greater than 0mg/g, and the content Cc of propylene carbonate in the positive electrode active material layer per unit mass is smaller than the content Ca of propylene carbonate in the negative electrode active material layer per unit mass.
2. A lithium ion battery according to claim 1, wherein: the double-sided density of the positive plate is 267-447g/m 2 。
3. A lithium ion battery according to claim 2, wherein: the content of propylene carbonate in the positive electrode active material layer per unit mass is 0.34. 0.34 mg/g < Cc < 5.71mg/g.
4. A lithium ion battery according to claim 3, wherein: the addition amount of the propylene carbonate in the positive electrode active material layer is 0.05-1wt% of the total mass of the positive electrode active material layer.
5. A lithium ion battery according to claim 3, wherein: the content of propylene carbonate in the positive electrode active material layer per unit mass is 3.17mg/g < Cc < 3.28mg/g.
6. A lithium ion battery according to claim 1, wherein: the surface density of the positive plate is 150-200g/m 2 。
7. The lithium ion battery of claim 6, wherein: the content of propylene carbonate in the negative electrode active material layer per unit mass is 1.91 mg/g < Ca < 15.52mg/g.
8. The lithium ion battery of claim 7, wherein: the propylene carbonate content per unit mass of the negative electrode active material layer was 10.27mg/g < Ca < 10.87mg/g.
9. The lithium ion battery of claim 7, wherein: the propylene carbonate is added to the negative electrode active material layer in an amount of 0.2 to 4wt% based on the total mass of the negative electrode active material layer.
10. A lithium ion battery according to claim 1, wherein: the positive electrode active material layer comprises a positive electrode active material comprising LiFePO 4 And LiNi x Co y Mn (1-x-y) O 2 Wherein 0.6.ltoreq.x < 1,0 < y < 0.4,0 < x+y < 1.
11. A lithium ion battery according to claim 1, wherein: the anode active material layer includes an anode active material including at least one of graphite, silicon oxide, and silicon carbon.
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