CN114464893A - Manufacturing method of square cylindrical composite titanium battery - Google Patents
Manufacturing method of square cylindrical composite titanium battery Download PDFInfo
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- CN114464893A CN114464893A CN202111524430.XA CN202111524430A CN114464893A CN 114464893 A CN114464893 A CN 114464893A CN 202111524430 A CN202111524430 A CN 202111524430A CN 114464893 A CN114464893 A CN 114464893A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 239000010936 titanium Substances 0.000 title claims abstract description 65
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011267 electrode slurry Substances 0.000 claims abstract description 22
- 238000004804 winding Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 66
- 238000007599 discharging Methods 0.000 claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 25
- 238000002347 injection Methods 0.000 claims description 23
- 239000007924 injection Substances 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005056 compaction Methods 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 12
- 241001312219 Amorphophallus konjac Species 0.000 claims description 10
- 235000001206 Amorphophallus rivieri Nutrition 0.000 claims description 10
- 229920001503 Glucan Polymers 0.000 claims description 10
- 229920002752 Konjac Polymers 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 10
- 239000000252 konjac Substances 0.000 claims description 10
- 235000010485 konjac Nutrition 0.000 claims description 10
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 10
- 239000001394 sodium malate Substances 0.000 claims description 10
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 239000006257 cathode slurry Substances 0.000 claims description 5
- 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 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 claims description 2
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 229910004764 HSV900 Inorganic materials 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/36—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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a novel square cylindrical composite titanium lithium battery manufacturing method, which comprises the steps of preparing negative electrode slurry and positive electrode slurry, coating the positive electrode slurry and the negative electrode slurry on a current collector with a conductive coating, drying the current collector through an oven to prepare positive and negative electrode coating pole pieces, pressing the positive and negative electrode coating pole pieces into compact positive and negative pole pieces through a roller press, cutting the compact positive and negative pole pieces into small-width pole pieces required by battery manufacturing, baking, winding, assembling, baking a battery core, injecting liquid, standing at high temperature, forming, sealing, dividing the volume, packaging and warehousing. The square cylindrical composite titanium battery manufactured by the invention has the advantages of super-long cycle life, high rate performance, excellent high and low temperature performance and super-good safety performance. In follow-up PACK assembling process, can be very big save the equipment cost, improve the performance of PACK module.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a manufacturing method of a square cylindrical composite titanium battery.
Background
Lithium ion batteries are divided according to an electrochemical system in the current market, mainly comprise lithium iron phosphate batteries, ternary batteries, lithium manganate batteries, lithium cobaltate batteries and the like, and are divided according to structures, mainly comprise square-shell batteries, cylindrical batteries and soft package batteries. Different electrochemical systems and structural batteries have the following disadvantages:
1. the lithium iron phosphate battery cannot be charged quickly, the charging time is as long as 2-5h, the charging time is too long, the low-temperature performance is poor, the battery capacity loss is 50-65% at the temperature of-20 ℃, the cycle life is short, and about 2000-2500 weeks, so that the product use is seriously influenced.
2. The ternary battery is unsafe and easy to ignite and explode, so that major safety accidents are caused, in addition, the ternary battery cannot be charged quickly, the charging time is too long, the cycle life of the ternary battery is poor, and about 1500-2000 weeks affect the use of products.
3. The lithium manganate battery has low energy density and poor cycle life.
4. Along with the continuous promotion of battery energy density, square battery or cylinder battery annotate the liquid time long, seriously influence production efficiency, annotate the liquid volume and be few, seriously influence battery cycle life.
5. The battery needs to carry out series-parallel connection between different monomers in the subsequent PACK use process to and weld the polar plate between the different monomers, compare with cylindrical structure, the stack between the battery is comparatively inconvenient with the location, precision and PACK cost when influence battery constitution unit.
Disclosure of Invention
The invention provides a manufacturing method of a square and cylindrical composite titanium battery, which can solve a series of problems of short cycle life, poor low-temperature performance, incapability of quick charging, poor safety, difficult liquid injection of a cylindrical or square battery, inconvenient assembly of a cylindrical battery PACK, high cost and the like of a lithium battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a manufacturing method of a square cylindrical composite titanium battery comprises the following steps:
s1, stirring: mixing and stirring a nanoscale composite lithium titanate material, a solvent NMP, a conductive agent and a binder by adopting a high-viscosity stirring process to prepare a negative electrode slurry; mixing and stirring a nickel cobalt lithium manganate ternary material or a lithium manganate material with a solvent NMP, a conductive agent and a binder to prepare a positive electrode slurry;
s2, coating: coating the positive and negative electrode slurry on a current collector with a conductive coating by an extrusion spraying or transfer coating machine, and drying by an oven to prepare a positive and negative electrode coating pole piece;
s3, rolling: pressing the positive and negative electrode coating pole pieces into compact positive and negative pole pieces by a roller press with a certain compaction density;
s4, slitting: cutting the rolled wide pole piece into a small-width pole piece required by the battery manufacturing by using a cutting machine;
s5, baking the pole piece: baking the cut positive and negative pole pieces at a specific temperature in vacuum;
s6, winding: winding the baked positive and negative pole pieces and the isolation film into a winding body bare cell by a winding machine in a full-tab winding mode;
s7, assembling: matching the winding body naked electric core with a square cylindrical structure, and assembling the winding body naked electric core into a monomer composite titanium electric core through a laser welding machine;
s8, baking the battery cell: placing the assembled monomer composite titanium electric core in a high vacuum oven for baking;
s9, injection: injecting a certain amount of electrolyte into the baked composite titanium monomer battery cell in a low vacuum-high pressure liquid injection mode to form a composite titanium battery;
s10, standing at high temperature: standing the composite titanium battery after liquid injection for a certain time at a certain temperature to enable the electrolyte to thoroughly infiltrate the pole piece and the diaphragm;
s11, formation: the composite titanium battery is continuously charged and discharged in an opening mode, the battery is thoroughly activated, and gas generated in formation is removed;
s12, sealing: sealing the composite titanium battery subjected to formation activation by adopting a screw plug to an exhaust port;
s13, capacity grading: putting the sealed battery on a grading cabinet, and charging and discharging according to a specific charging and discharging process to obtain a finished product composite titanium battery;
s14, packaging and warehousing: and classifying the finished composite titanium battery according to the capacity and the internal resistance, and packaging and warehousing.
Preferably, in the step 1, the particle size of the primary particles of the nano-scale composite lithium titanate material is D10 60~90nm，D50 250-300nm，D90 400~600nm，D99650-800 nm. The particle diameter of the secondary particles of the composite lithium titanate material synthesized by the primary particles is D10 ＞1.4um，5＜D50＜12um，D90 ＜40um。
The preparation method of the nano-scale composite lithium titanate material comprises the step of mixing a lithium source, a titanium source and water, wherein the lithium source is LiOH. H2One or more of O, lithium carbonate and lithium acetate, and the titanium source is TiO2·2H2O, and the mass ratio of the lithium source to the titanium source to the water is 2-3: 6-8: 20-25, and uniformly stirring; then spray drying is carried out until the water content of the material is below 5%, and then primary sintering is carried out to obtain a dry material; carrying out wet ball milling on the dry material, taking water as a solvent and zirconia balls as a ball milling medium, and grinding to obtain nano slurry; and (3) carrying out spray drying on the nano slurry again to obtain a spherical material, carrying out secondary sintering, and finally carrying out vacuum drying at 120-180 ℃ to remove water, wherein the water content of the material is controlled to be less than 200ppm, so as to obtain the lithium titanate material for the lithium ion battery.
Preferably, in the step 1, the anode slurry: the weight ratio of the solvent to the slurry is 45-55%, the weight ratio of the binder to the powder material is 2.0-5.0%, the weight ratio of the conductive agent to the powder material is 2.0-5.0%, and the weight ratio of the nano-scale composite lithium titanate material to the powder material is 90-96%.
Further preferably, the conductive agent is conductive carbon black (30-40 nm) (SUPER-P) or large particle graphite powder (6.5 μm) (KS-6), the solvent is methyl pyrrolidone, and the binder is HSV900 or Suwei 5130 in PVDF (linear crystalline polyvinylidene fluoride polymer).
Preferably, in the step 1, an additive is further added to the negative electrode slurry: the mass fraction of the additive accounts for 0.3-4% of the mass of the negative electrode slurry; the additive comprises a composition of sodium tripolyphosphate and sodium malate or weak acids such as citric acid and acetic acid, and the mass ratio of the sodium tripolyphosphate to the sodium malate is 1: (0.5-0.8).
Further preferably, in the step 1, in the negative electrode slurry, the additive includes konjac glucan, and the mass ratio of the sodium tripolyphosphate, the sodium malate, and the konjac glucan is 1: (0.5-0.8): (0.2-0.3).
Further preferably, in the step 1, the positive electrode slurry: the weight ratio of the solvent to the slurry is 30-45%, the weight ratio of the binder to the powder material is 2.0-5.0%, the weight ratio of the conductive agent to the powder material is 2.0-5.0%, and the weight ratio of the nickel cobalt lithium manganate ternary material or the lithium manganate material is 90-96%;
still more preferably, the conductive agent is conductive carbon black (30-40 nm) (SUPER-P) or large particle graphite powder (6.5 μm) (KS-6), and the binder is HSV900 or Suwei 5130 in PVDF (Linear crystalline polyvinylidene fluoride).
Preferably, in the step 1, a double-planet mixer is adopted for the cathode slurry and the anode slurry, so that the viscosity of the slurry can reach 15000mpa.s in the process of mixing the powder material;
in the step 3, the compaction density of the positive plate is 2.5-3.6 g/cm3The compaction density of the negative plate is 1.5-2.2 g/cm3。
Preferably, in the step 5, the pole piece is baked until the moisture of the positive pole piece is controlled within 300ppm, and the moisture of the negative pole piece is controlled within 1000 ppm.
Preferably, in the step 8, when the cell is baked, the assembled monomer composite titanium cell is placed in a high vacuum oven, the temperature is set to be 70-100 ℃, the vacuum is greater than 10pa, baking is carried out for 6-15 hours, the moisture of the positive pole piece is controlled within 100ppm, and the moisture of the negative pole piece is controlled within 500 ppm;
in the step 9, during liquid injection, the baked composite titanium monomer battery cell is injected with a liquid injection coefficient of 3-7 g/Ah at a low pressure of-65 KPa to-95 KPa and a high pressure of 0.1-0.5MPa to form a composite titanium battery;
in the step 10, standing at high temperature: standing the liquid-injected composite titanium battery for 36-168 hours at the temperature of 35-55 ℃, so that the electrode plate and the diaphragm are thoroughly soaked by the electrolyte, the polarization of the battery is reduced, and the multiplying power, low temperature, cycle performance and the like of the battery are improved.
Preferably, the square cylindrical composite titanium battery comprises a negative electrode assembly, a positive electrode assembly and a battery shell, wherein the negative electrode assembly is arranged at the tail end of the battery shell, the positive electrode assembly is arranged at the top end of the battery shell, a central tube is further arranged inside the battery shell, two ends of the central tube are clamped with the negative electrode assembly and the positive electrode assembly through connecting plungers, and the axis of the central tube coincides with the positive electrode assembly and the negative electrode assembly.
The invention has the following beneficial effects:
1. the molecular weight of HSV900 or 5130 is 100-kilo-molecular-weight organic matter, and the HSV900 or 5130 is used as a binder, so that compared with the common binder, the binding effect between active substances and a current collector can be greatly improved, and the performances of multiplying power, circulation and the like of a battery can be greatly improved.
The molecular weight of HSV900 or 5130 is 100-kilo-molecular-weight organic matter, and the HSV900 or 5130 is used as a binder, so that compared with the common binder, the binding effect between active substances and a current collector can be greatly improved, and the performances of multiplying power, circulation and the like of a battery can be greatly improved. The stirring of positive negative pole adopts double planet mixer for powder material is at the stirring in-process, and the thick liquids viscosity can be up to more than 15000mpa.s, is high viscosity stirring mode, can be fine, in less time, breaks up nanometer compound lithium titanate material and ternary material, forms highly even thick liquids, improves performances such as battery multiplying power, low temperature, circulation, also can improve battery uniformity by a wide margin simultaneously.
The negative electrode slurry is added with an additive, the additive comprises sodium tripolyphosphate, sodium malate and konjac glucan, the konjac glucan can help the slurry to form a stable network structure, the sodium tripolyphosphate and the sodium malate are filled in the network structure of the konjac glucan, and the slurry is in a stable state and is prevented from agglomerating due to the steric hindrance and the electrostatic repulsion force of the sodium tripolyphosphate and the sodium malate. And the sodium tripolyphosphate and the sodium malate can reduce the alkalinity of the slurry, further prevent the PVDF chemical bond of the binder from agglomerating, realize the deflocculation of the cathode slurry, and simultaneously prevent the active substances and other materials of the cathode from agglomerating in the storage process, thereby improving the fluidity of the cathode slurry, promoting the dispersion effect, and further improving the service life and the charge-discharge performance of the battery. In the manufacturing process of the negative electrode material, the konjac glucan can also play a role of a certain binding agent, so that the using amount of the binding agent is reduced.
2. In the step 3, the compaction density of the positive plate is 2.5-3.6 g/cm3The compaction density of the negative plate is 1.5-2.2 g/cm3. By controlling the compaction density of the positive and negative pole pieces, the composite titanium or ternary material particles are not crushed and damaged, the performance of the battery is influenced, and meanwhile, the distance between the composite titanium or ternary material particles is in an optimal state, so that the resistance of lithium ions in insertion and extraction can be greatly reduced, the polarization of the battery is greatly reduced, and the performances of the battery such as multiplying power, low temperature and circulation are improved.
3. The cycle life of the battery at normal temperature can reach more than 20000 times, and short plates with short cycle life of ternary batteries, lithium iron phosphate batteries and other systems are solved. The battery has the charge efficiency of over 90 percent and the discharge efficiency of up to 80 percent under the environment of minus 40 ℃, and solves the problem of low temperature difference of battery systems such as lithium iron phosphate and the like.
4. The battery can be charged and discharged with high multiplying power, the 10C charging and discharging efficiency is more than 90 percent, and the problem of quick charging and discharging of battery systems such as ternary batteries, lithium iron phosphate and the like is solved.
5. When the battery is subjected to tests such as needling, extrusion, overcharging, overdischarging, short circuit and the like according to the GB/T31485 plus 2015 power storage battery safety requirement and test method of the electric automobile, the battery does not catch fire, explode or leak liquid.
6. The battery adopts square cylinder structure, compares with cylinder or square structure, and hollow structure in the landing leg of its inside positive negative pole support adopts can provide bigger storage space for electrolyte, has increased the cycle life of battery, has also shortened the battery liquid injection time simultaneously greatly, has improved production efficiency. The accessories are restricted by the constraints of different shapes, the connection is more tight than a single structure, the internal parts are not loosened or displaced due to external reasons in the subsequent use process, and the stability of the subsequent operation of the battery is improved. Meanwhile, the square cylindrical structure is adopted, so that series-parallel connection assembly of the battery in subsequent PACK is facilitated, and the PACK cost is greatly saved.
Drawings
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
FIG. 1 is a schematic view of the overall structure of the present invention;
in the figure: the battery comprises a negative electrode assembly 1, a central pipe 2, a battery shell 3, a connecting plunger 4 and a positive electrode assembly 5.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
The square cylindrical composite titanium battery comprises a negative electrode assembly 1, a positive electrode assembly 5 and a battery shell 3, wherein the negative electrode assembly 1 is arranged at the tail end of the battery shell 3, the positive electrode assembly 5 is arranged at the top end of the battery shell 3, a central tube 2 is further arranged inside the battery shell 3, two ends of the central tube 2 are connected with the negative electrode assembly 1 and the positive electrode assembly 5 in a clamping mode through a connecting plunger 4, and the axis of the central tube 2 coincides with the positive electrode assembly 5 and the negative electrode assembly 1.
Embodiment 1 production of a novel square cylindrical composite titanium lithium battery
S1, stirring: stirring by adopting a high-viscosity stirring process, adding a solvent of methyl pyrrolidone (NMP) and a binder of linear crystalline polyvinylidene fluoride Polymer (PVDF) into a planetary stirring tank, revolving at 30RPM, dispersing at 850RPM, and stirring for 12 hours to prepare a glue solution. Adding a specific amount of conductive carbon black into the glue solution, revolving at 35RPM, dispersing at 1750RPM, and stirring for 2 h. And adding the nano-scale composite lithium titanate material, revolving at 35RPM, dispersing at 1750RPM, and stirring for 2h to prepare the cathode slurry. Adding solvent NMP, measuring binder PVDF, revolving at 30RPM, dispersing at 850RPM, and stirring for 12h to obtain glue solution. Adding a specific amount of conductive carbon black into the glue solution, revolving at 35RPM, dispersing at 1750RPM, and stirring for 2 h. And adding a nickel-cobalt-manganese ternary material or a lithium manganate material, revolving at 35RPM, dispersing at 1750RPM, and stirring for 2h to prepare the anode slurry.
S2, coating: coating the positive and negative electrode slurry on a current collector with a conductive coating by an extrusion spraying or transfer coating machine, and drying by an oven (the drying temperature is 65-115 ℃, so that the konjac glucan can be primarily denatured, and the konjac glucan forms a stable gel network by combining with the high-temperature baking of the later step S5, so that the stability of the slurry is ensured, and the uniformity control in the compaction process of the step S3 is facilitated) to prepare the positive and negative electrode coating pole piece.
S3, rolling: the positive electrode compaction adopts 3.1g/cm3The compaction of the negative electrode is 1.75 g/cm3And pressing the positive and negative electrode coating pole pieces into compact positive and negative pole pieces through a roller press.
S4, slitting: and (4) cutting the rolled wide pole piece into a small-width pole piece required by battery manufacturing by using a splitting machine.
S5, baking the pole piece: and (3) placing the cut positive and negative pole pieces in a high-temperature oven at a set temperature of 100 ℃ and a vacuum of 0.095MPa, and baking for 20 hours to control the water content of the positive pole piece to be within 300ppm and the water content of the negative pole piece to be within 1000 ppm.
S6, winding: and winding the baked positive and negative pole pieces and the isolation film into a winding body bare cell by a winding machine in a full-tab winding mode.
S7, assembling: and matching the naked electric core of the winding body with the square cylindrical structure, and assembling the naked electric core of the winding body into a monomer composite titanium electric core through a laser welding machine.
S8, baking the battery cell: and placing the assembled monomer composite titanium battery cell in a high-vacuum oven, setting the temperature at 70 ℃, baking for 6 hours at the vacuum of more than 10pa, and controlling the moisture of the positive pole piece to be within 100ppm and the moisture of the negative pole piece to be within 500 ppm.
S9, injection: and during liquid injection, injecting the baked composite titanium monomer battery cell at a low pressure of-95 KPa and a high pressure of 0.2MPa according to the liquid injection coefficient of 5g/Ah to obtain the composite titanium battery.
S10, standing at high temperature: and standing the composite titanium battery after liquid injection for 80 hours at the temperature of 45 ℃ to enable the electrolyte to thoroughly infiltrate the pole piece and the diaphragm.
S11, formation: through the opening mode, carry out lasting charge-discharge to compound titanium battery, thoroughly activate the battery, get rid of the gas that produces in the formation.
S12, sealing: and sealing the composite titanium battery subjected to formation activation by adopting a screw plug to an exhaust port.
S13, capacity grading: and (4) putting the sealed battery on a grading cabinet, and charging and discharging according to a specific charging and discharging process to obtain the finished product composite titanium battery.
S14, packaging and warehousing: and classifying the finished composite titanium battery according to the capacity and the internal resistance, and packaging and warehousing.
Wherein: in the step 1, the particle size of the nano-scale composite lithium titanate material is D10 60~90nm，D50 250-300nm，D90 400~600nm，D99 650~800nm。
The preparation method of the nano-scale composite lithium titanate material comprises the step of mixing a lithium source, a titanium source and water, wherein the lithium source is LiOH. H2One or more of O, lithium carbonate and lithium acetate, and the titanium source is TiO2·2H2O, and the mass ratio of the lithium source to the titanium source to the water is 2.5:7:22, and stirring uniformly; then spray drying is carried out until the water content of the material is below 5%, and then primary sintering is carried out to obtain a dry material; carrying out wet ball milling on the dry material, taking water as a solvent and zirconia balls as a ball milling medium, and grinding to obtain nano slurry; and (3) carrying out spray drying on the nano slurry again to obtain a spherical material, carrying out secondary sintering, and finally carrying out vacuum drying at 160 ℃ to remove water, wherein the water content of the material is controlled to be less than 200ppm, so as to obtain the lithium titanate material for the lithium ion battery.
And (3) negative electrode slurry: the weight ratio of the methyl pyrrolidone to the slurry is 48%, the weight ratio of the binder to the powder material is 2.5%, the weight ratio of the conductive agent to the powder material is 2.5%, and the weight ratio of the nano-scale composite lithium titanate material to the powder material is 95%.
The positive electrode slurry: the weight ratio of the solvent to the slurry is 35%, the weight ratio of the binder to the powder material is 2%, the weight ratio of the conductive agent to the powder material is 2%, and the weight ratio of the nickel-cobalt-manganese ternary material or the lithium manganate material is 96%.
Example 4 (Positive electrode sheet compacted density of 2.5 to 3.6 g/cm)3The compaction density of the negative plate is 1.5-2.2 g/cm3）
The difference from example 1 is that the positive electrode sheet and the negative electrode sheet are compacted in density in step 3.
Example 1: the compacted density of the positive plate is 3.1g/cm3The compacted density of the negative pole piece is 1.75 g/cm3；
Example 4-1: the compacted density of the positive plate is 3.1g/cm3The compacted density of the negative pole piece is 1.5g/cm3；
Example 4-2: the compacted density of the positive plate is 3.1g/cm3The compacted density of the negative pole piece is 2.2 g/cm3；
Examples 4 to 3: the compacted density of the positive plate is 3.1g/cm3The compacted density of the negative pole piece is 2.5 g/cm3；
Examples 4 to 4: the compacted density of the positive plate is 2.1g/cm3The compacted density of the negative pole piece is 1.85g/cm3；
Examples 4 to 5: the compacted density of the positive plate is 3.2g/cm3The compacted density of the negative pole piece is 1.85g/cm3；
Examples 4 to 6: the compacted density of the positive plate is 3.8g/cm3The compacted density of the negative pole piece is 1.85g/cm3；
The battery prepared according to the method has the following performances:
example 1: the 10C charging efficiency is up to 91.42 percent, the 10C discharging efficiency is up to 94.12 percent, the 2C charging and discharging cycle is 20000 weeks at normal temperature, and the capacity retention rate is more than 80 percent; -40 ℃, a 0.3C charging efficiency of 92%, and a 0.3C discharging efficiency of 81%.
Example 4-1: the 10C charging efficiency is 90.14 percent, the 10C discharging efficiency is 92.52 percent, the 2C charging and discharging cycle is 18500 weeks at normal temperature, and the capacity retention rate is more than 80 percent; -40 ℃, 0.3C charging efficiency 90.7%, 0.3C discharging efficiency 76.8%.
Example 4-2: the 10C charging efficiency is 90.04% and the 10C discharging efficiency is 90.77%, the capacity retention rate is more than 80% after the cycle of 18300 weeks at normal temperature; -40 ℃, a 0.3C charging efficiency of 89.87%, and a 0.3C discharging efficiency of 78.7%.
Examples 4 to 3: 67.45% of 10C charging efficiency, 62.2% of 10C discharging efficiency, 4600 weeks of 2C charging and discharging circulation at normal temperature, and the capacity retention rate is more than 80%; -40 ℃, 54% of 0.3C charging efficiency and 48% of 0.3C discharging efficiency.
Examples 4 to 4: 89.26% of 10C charging efficiency, 91.47% of 10C discharging efficiency, 16500 weeks of 2C charging and discharging circulation at normal temperature, and the capacity retention rate is more than 80%; -40 ℃, 0.3C charging efficiency 90.1%, 0.3C discharging efficiency 75.7%.
Examples 4 to 5: the 10C charging efficiency is up to 93.67%, the 10C discharging efficiency is up to 95.86%, the 2C charging and discharging cycle at normal temperature is 20000 weeks, and the capacity retention rate is more than 80%; -40 ℃, 0.3C charging efficiency 93.8%, 0.3C discharging efficiency 83.7%.
Examples 4 to 6: 56.95% of 10C charging efficiency, 61.72% of 10C discharging efficiency, 5350 weeks of 2C charging and discharging circulation at normal temperature, and more than 80% of capacity retention rate; -40 ℃, a 0.3C charging efficiency of 46.9%, and a 0.3C discharging efficiency of 52.1%.
From examples 4-1 to 4-6, it can be seen that: ensuring the compaction density of the positive plate to be 3.1-3.5 g/cm3The compacted density of the negative plate is 1.6-2.0 g/cm3The effect of (a) is the best.
Example 5 (injection coefficient of 3 to 7 g/Ah)
Example 1 was used as the basis, and the difference was that the injection coefficients were different in step 9
Example 1: the liquid injection coefficient is 5 g/Ah;
example 5-1: the liquid injection coefficient is 1 g/Ah;
example 5-2: the liquid injection coefficient is 2 g/Ah;
examples 5 to 3: the liquid injection coefficient is 6 g/Ah;
examples 5 to 4: the liquid injection coefficient is 7 g/Ah;
the battery prepared according to the method has the following performances:
example 1: the 10C charging efficiency is up to 91.42 percent, the 10C discharging efficiency is up to 94.12 percent, the 2C charging and discharging cycle is 20000 weeks at normal temperature, and the capacity retention rate is more than 80 percent; -40 ℃, a 0.3C charging efficiency of 92%, and a 0.3C discharging efficiency of 81%.
In the embodiment 5-1, the 10C charging efficiency is as high as 56.27%, the 10C discharging efficiency is as high as 62.52%, the 2C charging and discharging cycle at normal temperature is 1200 weeks, and the capacity retention rate is more than 80%; -40 ℃, a 0.3C charging efficiency of 43.5%, and a 0.3C discharging efficiency of 47.9%.
Example 5-2, the 10C charging efficiency is up to 68.62%, the 10C discharging efficiency is up to 69.45%, the 2C charging and discharging cycle at normal temperature is 3000 weeks, and the capacity retention rate is more than 80%; -40 ℃, 0.3C charging efficiency 52.61%, 0.3C discharging efficiency 58.92%.
In examples 5-3, the 10C charging efficiency is up to 91.42%, the 10C discharging efficiency is up to 94.12%, the 2C charging and discharging cycle is 22000 weeks at normal temperature, and the capacity retention rate is more than 80%; -40 ℃, a 0.3C charging efficiency of 92%, and a 0.3C discharging efficiency of 81%.
In examples 5-4, the 10C charging efficiency is up to 91.42%, the 10C discharging efficiency is up to 94.12%, the 2C charging and discharging cycle is 25000 weeks at normal temperature, and the capacity retention rate is more than 80%; -40 ℃, a 0.3C charging efficiency of 92%, and a 0.3C discharging efficiency of 81%.
The above embodiments are merely preferred technical solutions of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. The manufacturing method of the square cylindrical composite titanium battery is characterized by comprising the following steps of:
s1, stirring: mixing and stirring a nanoscale composite lithium titanate material, a solvent NMP, a conductive agent and a binder by adopting a high-viscosity stirring process to prepare a negative electrode slurry; mixing and stirring a nickel cobalt lithium manganate ternary material or a lithium manganate material with a solvent NMP, a conductive agent and a binder to prepare a positive electrode slurry;
s2, coating: coating the positive and negative electrode slurry on a current collector with a conductive coating by an extrusion spraying or transfer coating machine, and drying by an oven to prepare a positive and negative electrode coating pole piece;
s3, rolling: pressing the positive and negative coated pole pieces into compact positive and negative pole pieces by a roller press;
s4, slitting: cutting the rolled wide pole piece into a small-width pole piece required by the battery manufacturing by using a cutting machine;
s5, baking the pole piece: baking the cut positive and negative pole pieces;
s6, winding: winding the baked positive and negative pole pieces and the isolation film into a winding body bare cell by a winding machine in a full-tab winding mode;
s7, assembling: matching the winding body naked electric core with a square cylindrical structure, and assembling the winding body naked electric core into a monomer composite titanium electric core through a laser welding machine;
s8, baking the battery cell: placing the assembled monomer composite titanium electric core in a high vacuum oven for baking;
s9, injection: injecting electrolyte into the baked composite titanium monomer battery cell in a low vacuum-high pressure liquid injection mode to form a composite titanium battery;
s10, standing at high temperature: standing the composite titanium battery after liquid injection to enable the electrolyte to thoroughly infiltrate the pole piece and the diaphragm;
s11, formation: the composite titanium battery is continuously charged and discharged in an opening mode, the battery is thoroughly activated, and gas generated in formation is removed;
s12, sealing: sealing the composite titanium battery subjected to formation activation by adopting a screw plug to an exhaust port;
s13, capacity grading: putting the sealed battery on a grading cabinet, and charging and discharging according to a specific charging and discharging process to obtain a finished product composite titanium battery;
s14, packaging and warehousing: and classifying the finished composite titanium battery according to the capacity and the internal resistance, and packaging and warehousing.
2. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein in the step 1, the primary particles of the nano-scale composite lithium titanate material have a particle size D10 60~90nm，D50 250-300nm，D90 400~600nm，D99650~800nm；
The particle diameter of the secondary particles of the composite lithium titanate material synthesized by the primary particles is D10 ＞1.4um，5＜D50＜12um，D90＜40um；
The preparation method of the nano-scale composite lithium titanate material comprises the step of mixing a lithium source, a titanium source and water, wherein the lithium source is LiOH. H2One or more of O, lithium carbonate and lithium acetate, and the titanium source is TiO2·2H2O, and uniformly stirring, wherein the mass ratio of the lithium source to the titanium source to the water is 2-3: 6-8: 20-25; then spray drying is carried out until the water content of the material is below 5 percent, and then primary sintering is carried out to obtain dry materialFeeding; carrying out wet ball milling on the dry material, taking water as a solvent and zirconia balls as a ball milling medium, and grinding to obtain nano slurry; and (3) carrying out spray drying on the nano slurry again to obtain a spherical material, carrying out secondary sintering, and finally carrying out vacuum drying at 120-180 ℃ to remove water, wherein the water content of the material is controlled to be less than 200ppm, so as to obtain the lithium titanate material for the lithium ion battery.
3. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein in the step 1, the negative electrode slurry: the weight ratio of the solvent to the slurry is 45-55%, the weight ratio of the binder to the powder material is 2.0-5.0%, the weight ratio of the conductive agent to the powder material is 2.0-5.0%, and the weight ratio of the nano-scale composite lithium titanate material to the powder material is 90-96%.
4. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein in the step 1,
in the negative electrode slurry, an additive is also added: the mass fraction of the additive accounts for 0.3-4% of the mass of the negative electrode slurry; the additive comprises a composition of sodium tripolyphosphate and sodium malate or weak acids such as citric acid and acetic acid, and the mass ratio of the sodium tripolyphosphate to the sodium malate is 1: (0.5-0.8).
5. The method for manufacturing the square-cylindrical composite titanium battery according to claim 4, wherein in the step 1, the additive comprises konjac glucan, sodium tripolyphosphate, sodium malate and konjac glucan in a mass ratio of 1: (0.5-0.8): (0.2-0.3).
6. The method for manufacturing the square-cylindrical composite titanium battery according to claim 2, wherein in the step 1, the positive electrode slurry: the weight ratio of the solvent to the slurry is 30-45%, the weight ratio of the binder to the powder material is 2.0-5.0%, the weight ratio of the conductive agent to the powder material is 2.0-5.0%, and the weight ratio of the nickel cobalt lithium manganate ternary material or the lithium manganate material is 90-96%.
7. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein in the step 1, a double-planet stirrer is adopted for the cathode slurry and the anode slurry, so that the viscosity of the slurry can reach 15000mpa.s in the stirring process of the powder material;
in the step 3, the compaction density of the positive plate is 2.5-3.6 g/cm3The compaction density of the negative plate is 1.5-2.2 g/cm3。
8. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein in the step 5, the pole piece is baked until the moisture content of the positive pole piece is controlled within 300ppm and the moisture content of the negative pole piece is controlled within 1000 ppm.
9. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein in the step 8, when the battery core is baked, the assembled monomer composite titanium battery core is placed in a high-vacuum oven, the set temperature is 70-100 ℃, the vacuum is greater than 10pa, baking is carried out for 6-15 hours, the moisture of the positive pole piece is controlled within 100ppm, and the moisture of the negative pole piece is controlled within 500 ppm;
in the step 9, during liquid injection, the baked composite titanium monomer battery cell is injected with a liquid injection coefficient of 3-7 g/Ah at a low pressure of-65 KPa to-95 KPa and a high pressure of 0.1-0.5MPa to form a composite titanium battery;
in the step 10, standing at high temperature: standing the liquid-injected composite titanium battery for 36-168 hours at the temperature of 35-55 ℃, so that the electrode plate and the diaphragm are thoroughly soaked by the electrolyte, the polarization of the battery is reduced, and the multiplying power, low temperature, cycle performance and the like of the battery are improved.
10. The method for manufacturing the square-cylindrical composite titanium battery according to claim 1, wherein the square-cylindrical composite titanium battery comprises a negative electrode assembly (1), a positive electrode assembly (5) and a battery shell (3), and is characterized in that: the tail end at battery case (3) is installed in negative pole subassembly (1), and the top at battery case (3) is installed in positive pole subassembly (5), and battery case (3) inside still is equipped with center tube (2), the both ends of center tube (2) are through connecting plunger (4) and negative pole subassembly (1) and positive pole subassembly (5) joint, the axle center and positive pole subassembly (5), the coincidence of negative pole subassembly (1) three of center tube (2).
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