CN114497699A - Water-based lithium iron phosphate battery - Google Patents
Water-based lithium iron phosphate battery Download PDFInfo
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- CN114497699A CN114497699A CN202210118426.1A CN202210118426A CN114497699A CN 114497699 A CN114497699 A CN 114497699A CN 202210118426 A CN202210118426 A CN 202210118426A CN 114497699 A CN114497699 A CN 114497699A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 96
- 239000002002 slurry Substances 0.000 claims abstract description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011888 foil Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000013543 active substance Substances 0.000 claims abstract description 10
- 239000006256 anode slurry Substances 0.000 claims abstract description 10
- 238000005056 compaction Methods 0.000 claims abstract description 9
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 91
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- 239000011267 electrode slurry Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006257 cathode slurry Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004804 winding Methods 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000007731 hot pressing Methods 0.000 abstract description 3
- 238000003698 laser cutting Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000003292 glue Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 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 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a water-based lithium iron phosphate battery which comprises a positive plate, a diaphragm, a negative plate, electrolyte and a shell, and is characterized in that the positive plate comprises a positive current collector and positive slurry, the positive slurry comprises a positive active substance, conductive slurry, conductive carbon black, a water-based binder A, a water-based binder B and a water-based binder C, and the positive current collector is a light aluminum foil; the invention improves the dispersibility and stability of the anode slurry, improves the bonding property of the anode plate and the flexibility of the anode plate, improves the compaction density so as to improve the energy density, and has better flexibility of the pole piece, thereby improving the yield and the production efficiency of rolling, laser cutting, winding and hot pressing; the problems of scratch leakage and pole piece cracking caused by quick drying of the slurry are solved, and the internal resistance of the battery is reduced by the optical aluminum foil.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a water-based lithium iron phosphate battery.
Background
Compared with lead-acid batteries, nickel-metal hydride batteries and nickel-cadmium batteries, lithium ion batteries have the advantages of higher energy density, small self-discharge, long cycle life and the like, and are widely applied to the fields of consumer electronics and power batteries at present. Currently, the positive electrode slurry of the lithium ion battery generally adopts a fluorine-containing polymer such as polyvinylidene fluoride as a binder and NMP (N-methyl pyrrolidone) as a solvent. Because the organic solvent is easy to cause environmental pollution and harm to the health of operators, the cost input is increased to recover the organic solvent in the coating and drying process, and meanwhile, the cost of the NMP is higher, so that the production cost of the battery is increased. Therefore, research and development have been conducted on an aqueous positive electrode binder system, which can prevent environmental pollution and reduce production costs.
The water-based anode adopts deionized water as a solvent, and the binder adopts a water-based binder, but the water-based anode also has certain limitation in practical application and has the following problems:
(1) deionized water is used as a solvent, so that the dispersion of the positive electrode is difficult, the dispersion of slurry is difficult, and the stability is poor;
(2) during coating, on one hand, the slurry is dried quickly, so that scratches and foil leakage are caused; on the other hand, cracking powder dropping can be slightly improved by increasing the using amount of the binder and reducing the coating surface density, but the energy density is reduced;
(3) the pole piece is brittle during rolling, and although the flexibility of the pole piece can be slightly improved by reducing the compaction density, the energy density is also reduced;
(4) and the lamination process is adopted, so that the production efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a water-based lithium iron phosphate battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a water-based lithium iron phosphate battery comprises a positive plate, a diaphragm, a negative plate, electrolyte and a shell, wherein the positive plate comprises a positive current collector and positive slurry, the positive slurry comprises a positive active substance, conductive slurry, conductive carbon black, a water-based binder A, a water-based binder B and a water-based binder C, and the positive current collector is a light aluminum foil;
the weight ratio of the positive active material to the conductive slurry to the conductive carbon black to the water-based binder A to the water-based binder B to the water-based binder C is 93-96: 0.5-1.5: 0.2-1: 1.5-3: 0.5-1;
the aqueous conductive slurry is carbon nanotube slurry or graphene conductive slurry;
the conductive carbon black is superconducting carbon black, ketjen black or SP;
the aqueous binder A is an acrylate multipolymer, and the main chain is-C-C-main chain, so that the binder has good chain rotation property; the introduction of functional groups such as carboxyl and the like and smaller particle size show excellent dispersion stability to the lithium iron phosphate material; the existence of the polar functional side group enables the adhesive to show excellent bonding performance;
the aqueous binder B is a copolymer of acrylic acid and acrylonitrile;
the water-based binder C is acrylate, and the long carbon chain and the short carbon chain in the acrylate are respectively 50-80% and 20-50%.
Preferably, a toughening agent is also added into the aqueous binder B.
Preferably, the preparation method of the cathode slurry comprises the following steps:
s1, adding a water-based binder A, a water-based binder B and deionized water into a stirring tank according to a proportion, setting the stirring speed to be 10-20 revolutions per minute, setting the dispersion speed to be 100-600 revolutions per minute, and stirring for 10-30 min;
s2, adding the water-based conductive slurry and the conductive agent into a stirring tank according to a ratio, setting the stirring speed to be 30 revolutions per minute and the dispersion speed to be 2000 revolutions per minute, and stirring for 120 min;
s3, adding the positive active material into a stirring tank according to a proportion, setting the stirring speed to be 10-30 revolutions per minute, and stirring for 60 min; the solid content is 73-80%;
s4, adding deionized water, setting the stirring speed to be 10-30 revolutions per minute, setting the dispersion speed to be 800-1500 revolutions per minute, and stirring for 30 min; the solid content is 65-72%;
s5, adding deionized water and the mixed solution, setting the stirring speed to be 10-30 revolutions per minute, setting the dispersion speed to be 1500-2500 revolutions per minute, and stirring for 120 min; the mixed solution comprises NMP, deionized water and PC according to the weight ratio of 0.7-1: 0.01-0.03, wherein the addition amount of the NMP is 3-10 wt% of the positive active material;
s6, adding a dewatering binder C, setting the stirring speed to be 10-30 revolutions per minute, setting the dispersion speed to be 100-500 revolutions per minute, and stirring for 30 min;
s7, reverse defoaming;
and S8, detecting the viscosity, the fineness and the solid content of the slurry, adjusting the viscosity value of the slurry, and finishing the preparation of the anode slurry.
Preferably, the thickness of the positive current collector coated on the positive plate is 12-18 μm, and the density of a single-side coating surface is 1.5-2 g/100cm2And the rolling compaction density of the positive plate is 2.3-2.45 g/cc.
Preferably, the tensile strength of the positive electrode current collector is greater than 200Mpa, and the elongation is greater than 2.0%.
Preferably, the preparation method of the negative electrode sheet is as follows:
mixing natural graphite, mesocarbon microbeads, conductive carbon black, SBR and CMC in a weight ratio of 90.5: 5: 1: 3.5 with deionized water to prepare cathode slurry; and uniformly coating the negative electrode slurry on a copper foil with the thickness of 9 mu m, and then drying, rolling and cutting into strips at the temperature of 110 ℃ to prepare the negative electrode plate.
Compared with the prior art, the invention has the following advantages and positive effects:
(1) the stability of the positive electrode slurry is improved through the toughening agent;
(2) the three binders are mixed for use, so that the using amount of the binders can be reduced, the binding property of the pole piece and the flexibility of the positive pole piece can be improved, the problem of cracking and material falling during coating is solved, the compaction density is improved, the energy density is improved, the flexibility of the pole piece is good, and the yield and the production efficiency of rolling, laser cutting, winding and hot pressing can be improved; specifically, the aqueous binder A has the function of preventing slurry from settling, the aqueous binder B has the main function of bonding, the aqueous binder C has the main function of improving flexibility, and the aqueous binder C has the secondary function of bonding, so that the bonding effect is far smaller than that of the aqueous binder B;
(3) the long-range and short-range conductive network is formed by the aqueous conductive slurry and the carbon black, so that the conductivity is improved, and the consumption of a conductive agent is reduced;
(4) the solvent additive has a higher melting point and has the moisture retention property of the slurry during coating, so that the problem of scratching and foil leakage caused by quick drying of the slurry is solved; when the pole piece is dried, the solvent additive is remained in the pole piece due to the higher melting point of the solvent additive, so that the problem of pole piece cracking is solved, and the flexibility of the pole piece is improved;
(5) the optical aluminum foil reduces the internal resistance of the cell.
Detailed Description
The present invention will be further described with reference to specific embodiments for making the objects, technical solutions and advantages of the present invention more apparent, but the present invention is not limited to these examples. It should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment. In the invention, all parts and percentages are mass units, and the adopted equipment, raw materials and the like can be purchased from the market or are commonly used in the field. The methods in the following examples are conventional in the art unless otherwise specified.
The batteries prepared in the following examples and comparative examples were subjected to performance tests in accordance with GB/T31484-2015 and GB/T31486-2015 standards.
The following calculation formula of energy density of the batteries in examples and comparative examples:
energy density is discharge capacity multiplied by plateau voltage/cell weight
Plateau voltage of 3.2V
Example 1
(1) Positive plate
The positive plate comprises a positive current collector and positive slurry, wherein the positive slurry comprises a positive active substance, conductive slurry, conductive carbon black, a water-based aqueous binder A, a water-based aqueous binder B and a water-based aqueous binder C, and the positive current collector is a smooth aluminum foil;
the weight ratio of the positive active substance to the conductive slurry to the conductive carbon black to the water-based binder A to the water-based binder B to the water-based binder C is 94.5: 1.1: 0.5: 2.6: 0.7: 0.8;
the aqueous conductive slurry is carbon nanotube slurry;
the conductive carbon black is superconducting carbon black, ketjen black and SP;
the aqueous binder A is an acrylate multipolymer, and the main chain is-C-C-main chain, so that the binder has good chain rotation property; the introduction of functional groups such as carboxyl and the like and smaller particle size show excellent dispersion stability to the lithium iron phosphate material; the existence of the polar functional side group enables the adhesive to show excellent bonding performance;
the aqueous binder B is a copolymer of acrylic acid and acrylonitrile;
the water-based binder C is acrylate, and the long carbon chain and the short carbon chain in the acrylate are respectively 50-80% and 20-50%.
The water-based binder B is also added with a toughening agent.
The preparation method of the anode slurry comprises the following steps:
s1, adding a water-based binder A, a water-based binder B and deionized water into a stirring tank according to a proportion, setting the stirring speed to be 15 revolutions per minute and the dispersion speed to be 350 revolutions per minute, and stirring for 20 min;
s2, adding the water-based conductive slurry and the conductive agent into a stirring tank according to a ratio, setting the stirring speed to be 30 revolutions per minute and the dispersion speed to be 2000 revolutions per minute, and stirring for 120 min;
s3, adding the positive active material into a stirring tank according to a proportion, setting the stirring speed to be 20 revolutions per minute, and stirring for 60 min; the solid content is 76.5 percent;
s4, adding deionized water, setting the stirring speed to be 20 revolutions per minute and the dispersing speed to be 1050 revolutions per minute, and stirring for 30 min; solid content 68.5%;
s5, adding deionized water and the mixed solution, setting the stirring speed to be 20 revolutions per minute and the dispersing speed to be 1500-2500 revolutions per minute, and stirring for 120 min; the mixed solution comprises NMP, deionized water and PC according to the weight ratio of 0.7-1: 0.01-0.03, wherein the addition amount of the NMP is 3-10 wt% of the positive active material;
s6, adding a dewatering binder C, setting the stirring speed to be 10-30 r/min, setting the dispersion speed to be 100-;
s7, reverse defoaming;
and S8, detecting the viscosity, the fineness and the solid content of the slurry, adjusting the viscosity value of the slurry, and finishing the preparation of the anode slurry.
Uniformly coating the positive electrode slurry on a positive electrode current collector with the thickness of 15 mu m, wherein the surface density of single-side coating is 1.6g/100cm2And the rolled compaction density of the positive plate is 2.38 g/cc.
(2) Preparation of the negative electrode
Natural graphite (average particle size 12 μm, tap density 1.3 g/cm)3) MCMB (average particle size 9 μm, tap density 1.5 g/cm)3) Mixing the conductive carbon black, SBR and CMC in the weight ratio of 90.5 to 5 to 1 to 3.5 with deionized water to prepare negative electrode slurry, coating the negative electrode slurry on 9 micron copper foil, drying at 110 deg.c, rolling, cutting to prepare negative electrode sheet.
(3) Preparation of roll cores
And (3) winding the positive plate and the negative plate prepared in the steps (1) and (2) and the ceramic coating diaphragm (7+3) into a winding core.
(4) Preparation of the electrolyte
Mixing LiPF6(concentration of 1 mol/l) and additive VC (1%) were dissolved in a mixed solvent of PC (propylene carbonate)/EC (ethylene carbonate)/DMC (dimethyl carbonate)/EP (ethyl propionate) 3: 2: 3 (volume ratio) to form an electrolyte.
(5) Assembly of a battery
And (4) placing the winding core obtained in the step (3) into a shell, and then injecting the electrolyte prepared in the step (4) to prepare the water-system lithium iron phosphate battery.
Example 2
(1) Positive plate
The positive plate comprises a positive current collector and positive slurry, wherein the positive slurry comprises a positive active substance, conductive slurry, conductive carbon black, a water-based binder A, a water-based binder B and a water-based binder C, and the positive current collector is a smooth aluminum foil;
the weight ratio of the positive active substance to the conductive slurry to the conductive carbon black to the aqueous binder A to the aqueous binder B to the aqueous binder C is 96: 0.5: 1: 1.5: 0.5: 1;
the aqueous conductive slurry is carbon nanotube slurry or graphene conductive slurry;
the conductive carbon black is superconducting carbon black, ketjen black or SP;
the aqueous binder A is an acrylate multipolymer, and the main chain is-C-C-main chain, so that the binder has good chain rotation property; the introduction of functional groups such as carboxyl and the like and smaller particle size show excellent dispersion stability to the lithium iron phosphate material; the existence of the polar functional side group enables the adhesive to show excellent bonding performance;
the aqueous binder B is a copolymer of acrylic acid and acrylonitrile;
the water-based binder C is acrylate, and the long carbon chain and the short carbon chain in the acrylate are respectively 50-80% and 20-50%.
The water-based binder B is also added with a toughening agent.
The preparation method of the positive electrode slurry comprises the following steps:
s1, adding a water-based binder A, a water-based binder B and deionized water into a stirring tank according to a proportion, setting the stirring speed to be 20 revolutions per minute and the dispersion speed to be 100 revolutions per minute, and stirring for 30 min;
s2, adding the water-based conductive slurry and the conductive agent into a stirring tank according to a ratio, setting the stirring speed to be 30 revolutions per minute and the dispersion speed to be 2000 revolutions per minute, and stirring for 120 min;
s3, adding the positive active material into a stirring tank according to a proportion, setting the stirring speed to be 30 revolutions per minute, and stirring for 60 min; the solid content is 80 percent;
s4, adding deionized water, setting the stirring speed to be 30 revolutions per minute, setting the dispersion speed to be 800 revolutions per minute, and stirring for 30 min; solid content 72%;
s5, adding deionized water and the mixed solution, setting the stirring speed to be 30 revolutions per minute and the dispersing speed to be 1500 revolutions per minute, and stirring for 120 min; the mixed solution comprises NMP, deionized water and PC according to the weight ratio of 0.7: 1: 0.01, wherein the addition amount of the NMP is 10 wt% of the positive electrode active material;
s6, adding a dewatering binder C, setting the stirring speed to be 30 revolutions per minute and the dispersing speed to be 100 revolutions per minute, and stirring for 30 min;
s7, reverse defoaming;
and S8, detecting the viscosity, the fineness and the solid content of the slurry, adjusting the viscosity value of the slurry, and finishing the preparation of the anode slurry.
Uniformly coating the positive electrode slurry on a positive electrode current collector with the thickness of 18 mu m, wherein the surface density of single-side coating is 1.5g/100cm2And the rolled compaction density of the positive plate is 2.45 g/cc.
The other preparation steps were the same as in example 1.
Example 3
(1) Positive plate
The positive plate comprises a positive current collector and positive slurry, wherein the positive slurry comprises a positive active substance, conductive slurry, conductive carbon black, a water-based binder A, a water-based binder B and a water-based binder C, and the positive current collector is a smooth aluminum foil;
the weight ratio of the positive active substance to the conductive slurry to the conductive carbon black to the aqueous binder A to the aqueous binder B to the aqueous binder C is 93: 1.5: 0.2: 3: 0.5: 1;
the aqueous conductive slurry is carbon nanotube slurry or graphene conductive slurry;
the conductive carbon black is superconducting carbon black, ketjen black or SP;
the aqueous binder A is an acrylate multipolymer, and the main chain is-C-C-main chain, so that the binder has good chain rotation property; the introduction of functional groups such as carboxyl and the like and smaller particle size show excellent dispersion stability to the lithium iron phosphate material; the existence of the polar functional side group enables the adhesive to show excellent bonding performance;
the aqueous binder B is a copolymer of acrylic acid and acrylonitrile;
the water-based binder C is acrylate, and the long carbon chain and the short carbon chain in the acrylate are respectively 50-80% and 20-50%.
The water-based binder B is also added with a toughening agent.
The preparation method of the positive electrode slurry comprises the following steps:
s1, adding a water-based binder A, a water-based binder B and deionized water into a stirring tank according to a proportion, setting the stirring speed to be 10 revolutions per minute and the dispersion speed to be 600 revolutions per minute, and stirring for 10 min;
s2, adding the water-based conductive slurry and the conductive agent into a stirring tank according to a ratio, setting the stirring speed to be 30 revolutions per minute and the dispersion speed to be 2000 revolutions per minute, and stirring for 120 min;
s3, adding the positive active material into a stirring tank according to a proportion, setting the stirring speed to be 10 revolutions per minute, and stirring for 60 min; the solid content is 80 percent;
s4, adding deionized water, setting the stirring speed to be 10 revolutions per minute and the dispersing speed to be 1500 revolutions per minute, and stirring for 30 min; the solid content is 65%;
s5, adding deionized water and the mixed solution, setting the stirring speed to be 10 revolutions per minute and the dispersing speed to be 2500 revolutions per minute, and stirring for 120 min; the mixed solution comprises NMP, deionized water and PC according to the weight ratio of 0.7: 1: 0.01, wherein the addition amount of the NMP is 3 wt% of the positive electrode active material;
s6, adding the dewatering binder C, setting the stirring speed to be 10 revolutions per minute and the dispersing speed to be 500 revolutions per minute, and stirring for 30 min;
s7, reverse defoaming;
and S8, detecting the viscosity, the fineness and the solid content of the slurry, adjusting the viscosity value of the slurry, and finishing the preparation of the anode slurry.
Uniformly coating the positive electrode slurry on a positive electrode current collector with the thickness of 12 mu m, wherein the surface density of single-side coating is 2.0g/100cm2And the rolled compaction density of the positive plate is 2.30 g/cc.
The other preparation steps were the same as in example 1.
Comparative example 1
No toughening agent was added, and the other conditions and preparation method were the same as in example 1.
Comparative example 2
The amount of the aqueous binder B added was adjusted to 0, and other conditions and the preparation method were the same as in example 1.
Comparative example 3
The amount of the aqueous binder C added was adjusted to 0, and other conditions and the preparation method were the same as in example 1.
Comparative example 4
Preparing a positive electrode slurry according to the method of example 1 in patent 201210275706. X;
(1) preparing a premixed solution: weighing 40% of a positive electrode active material (lithium iron phosphate), 10% of a carbon nano tube, 5% of Super-P, 3% of a water-based binder and 42% of deionized water according to mass percentage, wherein the water-based binder comprises the following components in percentage by mass: 30% of methyl cellulose, 30% of sodium polyacrylate and 40% of styrene-butadiene latex, adding deionized water accounting for 60% of the total mass of the deionized water and a water-based binder into a planetary slurry stirrer, and stirring at a low speed of 25r/min for 30min to obtain a premixed solution, wherein the low-speed stirring speed is revolution and 500r/min rotation;
(2) preparing conductive glue solution: adding carbon nano tube and conductive agent into the premixed liquid, and stirring at high speed for 60min to obtain conductive glue solution, wherein the high-speed stirring speed is revolution at 50r/min and rotation at 2500 r/min.
(3) Primary dispersion: and grinding the conductive glue solution in a colloid mill to the fineness of 6 mu m.
(4) And (3) secondary dispersion: and adding the ground conductive glue solution, the positive active substance and the rest deionized water into a planetary slurry stirrer, and stirring at a high speed of revolution of 20r/min and rotation of 1800r/min until the fineness is 30 mu m to obtain a coarse slurry.
(5) Defoaming and standing: and vacuumizing the crude slurry for 30min, wherein the relative vacuum degree of vacuumizing is-92 KPa, and standing for 10min after vacuumizing to obtain the aqueous anode slurry of the lithium ion battery.
Other conditions and preparation method were the same as in example 1.
Comparative example 5
Preparing a positive plate according to the method of example 1 in patent 201510723952.0;
the lithium ion battery aqueous positive electrode composite current collector of the comparative example is prepared by the preparation method comprising the following steps:
1) adding 1kg of adhesive polyvinylidene fluoride (PVDF) into 20kg of solvent N-methyl pyrrolidone, and uniformly mixing to obtain an adhesive solution;
2) adding 9kg of conductive agent Super P into the binder solution prepared in the step 1), uniformly mixing, grinding and emulsifying for 2h by adopting grinding balls with the particle size of 0.4mm at the rotating speed of 1000rpm, defoaming for 8h, and sieving by using a 200-mesh sieve to obtain conductive slurry;
3) uniformly coating the conductive slurry prepared in the step 2) on two surfaces of an aluminum foil of a positive current collector by adopting a gravure printing machine, wherein the thickness of the aluminum foil is 20 mu m, and the coating surface density is 2g/m2And drying at 120 ℃ to obtain the product.
The positive plate comprises the above-mentioned lithium ion battery aqueous positive composite current collector and a positive active material coated on two surfaces of the lithium ion battery aqueous positive composite current collector, the lithium ion battery aqueous positive composite current collector comprises a current collector aluminum and conductive coatings coated on two surfaces of an aluminum foil, and the positive active material comprises the following components in percentage by weight: 95% of lithium iron phosphate, 2% of Super P, 2% of acrylamide-acrylonitrile copolymer and 1% of sodium carboxymethylcellulose.
The preparation method of the positive plate comprises the following steps of dissolving 42g of sodium carboxymethylcellulose in 1500g of water, adding 600g of acrylamide-acrylonitrile copolymer, uniformly mixing, adding 126g of super P, uniformly mixing, adding 4000g of lithium iron phosphate, uniformly mixing, adjusting the viscosity to be 5000 mPa.s, defoaming and filtering to obtain positive slurry, wherein the solid content of the obtained positive slurry is 50.8%, and uniformly coating the positive slurry on the aqueous positive composite current collector of the lithium ion battery by using an extrusion coating machine to obtain the positive plate.
Other conditions and preparation method are the same as example 1.
Comparative example 6
Preparing a positive plate according to the method of example 1 in patent 201710026337.3;
the preparation of the aqueous positive electrode slurry comprises the following steps:
step one, adding 0.4 part by weight of polyvinylpyrrolidone (PVP), 0.5 part by weight of ethylene carbonate and 10 parts by weight of deionized water into a stirrer, stirring at medium speed of 800rpm for 0.5h, and uniformly stirring to obtain a glue solution A;
step two, adding 5 parts by weight of LA133 and 40 parts by weight of deionized water into a stirrer, stirring at medium speed of 800rpm for 0.5h, and uniformly stirring to obtain a glue solution B;
step three, adding the glue solution A, 2 parts by weight of conductive carbon black and 1 part by weight of conductive graphite into the glue solution B, and stirring at a high speed of 1500rpm for 90 min;
step four, sequentially adding 92 parts by weight of nano lithium iron phosphate into a stirrer in equal amount, wherein the stirring speed is 500rpm when mixing is started, and after the mixture and the glue solution are initially mixed, the stirring speed is increased to high-speed dispersion, wherein the high-speed dispersion speed is 1800 rpm; high-speed dispersion time is 150 min;
step five, adding 25 parts by weight of deionized water to adjust the viscosity of the slurry to 5100 mpas;
and step six, vacuumizing to-0.085 MPa, defoaming, and filtering by using a filter screen to obtain the aqueous anode slurry.
Other conditions and preparation method were the same as in example 1.
Comparative example 7
Preparing a positive plate according to the method of example 1 in patent 201811215720.4;
selecting median particle diameter D50Lithium iron phosphate with the particle size of 3 mu m is taken as a main material of the anode slurry, a conductive agent is conductive carbon black, and a binder is an AB double-component aqueous binder provided by the invention;
wherein the AB two-component aqueous binder comprises a component A and a component B; component A is a mixture of carboxypropylmethylcellulose and polyacrylic acid, and component B is polyacrylic acid.
Firstly, respectively weighing 1722g (solid content is 5%) of glue A (namely the binder of the component A), 1000g of deionized water and 300g of conductive carbon black, and stirring for 2 hours at a stirring speed of 3500 rpm;
then adding 7000g of main material lithium iron phosphate of the positive electrode slurry twice, stirring for 1 hour at the stirring speed of 2000rpm, and then stirring for 3 hours at the speed of 3500 rpm;
then, adding 289g (solid content is 35%) of glue B (namely the binder of the component B) and 750g of deionized water after vacuumizing;
finally, the mixture was stirred under vacuum for 1 hour at a stirring speed of 1000 rpm. The slurry had a solids content of 67.7%, a fineness of 30 μm and a viscosity of 7600 cps.
The single-side coating surface density of the positive electrode slurry coated on the positive electrode current collector (such as aluminum foil) is 1.6g/m2The coating rate was 2m/s and the coating temperatures were 80, 110 and 90 ℃ respectively.
Other conditions and preparation method were the same as in example 1.
The lithium ion batteries of examples 1 to 3 and comparative examples 1 to 6 were each subjected to performance measurement, and the results are shown in table 1.
TABLE 1 measurement results of Performance of lithium ion batteries of examples 1 to 3 and comparative examples 1 to 7
From the results in table 1 above, it can be seen from examples 1 to 3 and comparative example 1 that the dispersibility and stability of the positive electrode slurry are improved by the toughening agent, and the cycle life of the battery is further improved; as can be seen from the examples 1-3 and the comparative examples 2 and 3, the invention mixes the three binders for use, solves the problem of cracking and material dropping during coating, improves the compaction density so as to improve the energy density, has good flexibility of the pole piece, and can improve the yield and the production efficiency of rolling, laser cutting, winding and hot pressing; from the examples 1-3, the long-range and short-range conductive networks are formed by the aqueous conductive slurry and the carbon black, so that the conductivity is improved, and the consumption of the conductive agent is reduced; the invention greatly improves the energy density of the lithium iron phosphate battery through the synergistic effect of the specific formula and the process, and simultaneously improves the discharge capacity, the cycle life and other performances of the battery; as can be seen from examples 1 to 3 and comparative examples 4 to 7, the comprehensive technical effect of the present invention is significantly improved compared to the prior art.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (6)
1. A water-based lithium iron phosphate battery comprises a positive plate, a diaphragm, a negative plate, electrolyte and a shell, and is characterized in that the positive plate comprises a positive current collector and positive slurry, the positive slurry comprises a positive active substance, conductive slurry, conductive carbon black, a water-based binder A, a water-based binder B and a water-based binder C, and the positive current collector is a light aluminum foil;
the weight ratio of the positive active material to the conductive slurry to the conductive carbon black to the water-based binder A to the water-based binder B to the water-based binder C is 93-96: 0.5-1.5: 0.2-1: 1.5-3: 0.5-1;
the aqueous conductive slurry is carbon nanotube slurry or graphene conductive slurry;
the conductive carbon black is superconducting carbon black, ketjen black or SP;
the aqueous binder A is an acrylate multipolymer, and the main chain is-C-C-main chain, so that the binder has good chain rotation property; the introduction of functional groups such as carboxyl and the like and smaller particle size show excellent dispersion stability to the lithium iron phosphate material; the existence of the polar functional side group enables the adhesive to show excellent bonding performance;
the aqueous binder B is a copolymer of acrylic acid and acrylonitrile;
the water-based binder C is acrylate, and the long carbon chain and the short carbon chain in the acrylate are respectively 50-80% and 20-50%.
2. The water-based lithium iron phosphate battery according to claim 1, wherein a toughening agent is further added to the aqueous binder B.
3. The water-based lithium iron phosphate battery according to claim 1, wherein the preparation method of the positive electrode slurry comprises the following steps:
s1, adding a water-based binder A, a water-based binder B and deionized water into a stirring tank according to a proportion, setting the stirring speed to be 10-20 revolutions per minute, setting the dispersion speed to be 100-600 revolutions per minute, and stirring for 10-30 min;
s2, adding the water-based conductive slurry and the conductive agent into a stirring tank according to a ratio, setting the stirring speed to be 30 revolutions per minute and the dispersion speed to be 2000 revolutions per minute, and stirring for 120 min;
s3, adding the positive active material into a stirring tank according to a proportion, setting the stirring speed to be 10-30 revolutions per minute, and stirring for 60 min; the solid content is 73-80%;
s4, adding deionized water, setting the stirring speed to be 10-30 revolutions per minute, setting the dispersion speed to be 800-1500 revolutions per minute, and stirring for 30 min; the solid content is 65-72%;
s5, adding deionized water and the mixed solution, setting the stirring speed to be 10-30 revolutions per minute, setting the dispersion speed to be 1500-2500 revolutions per minute, and stirring for 120 min; the mixed solution comprises NMP, deionized water and PC according to the weight ratio of 0.7-1: 0.01-0.03, wherein the addition amount of the NMP is 3-10 wt% of the positive active material;
s6, adding a dewatering binder C, setting the stirring speed to be 10-30 revolutions per minute, setting the dispersion speed to be 100-500 revolutions per minute, and stirring for 30 min;
s7, reverse defoaming;
and S8, detecting the viscosity, the fineness and the solid content of the slurry, adjusting the viscosity value of the slurry, and finishing the preparation of the anode slurry.
4. The water-based lithium iron phosphate battery according to claim 1, wherein the thickness of the positive current collector coated on the positive electrode sheet is 12 to 18 μm, and the single-side coating surface density is 1.5 to 2g/100cm2And the rolling compaction density of the positive plate is 2.3-2.45 g/cc.
5. The water-based lithium iron phosphate battery according to claim 4, wherein the positive electrode current collector has a tensile strength of greater than 200Mpa and an elongation of greater than 2.0%.
6. The water-based lithium iron phosphate battery according to claim 1, wherein the negative electrode sheet is prepared by a method comprising:
mixing natural graphite, mesocarbon microbeads, conductive carbon black, SBR and CMC in a weight ratio of 90.5: 5: 1: 3.5 with deionized water to prepare cathode slurry; and uniformly coating the negative electrode slurry on a 9-micron copper foil, and then drying, rolling, slitting and cutting at the temperature of 110 ℃ to prepare the negative electrode sheet.
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