CN113964383B - Positive electrode material additive for lithium ion battery, preparation method and application thereof - Google Patents
Positive electrode material additive for lithium ion battery, preparation method and application thereof Download PDFInfo
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- CN113964383B CN113964383B CN202111074531.1A CN202111074531A CN113964383B CN 113964383 B CN113964383 B CN 113964383B CN 202111074531 A CN202111074531 A CN 202111074531A CN 113964383 B CN113964383 B CN 113964383B
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- ion battery
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- lithium
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- 239000000654 additive Substances 0.000 title claims abstract description 97
- 230000000996 additive effect Effects 0.000 title claims abstract description 97
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 24
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 24
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 24
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 45
- 239000002109 single walled nanotube Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 description 43
- 239000011267 electrode slurry Substances 0.000 description 43
- 238000012360 testing method Methods 0.000 description 37
- 238000002474 experimental method Methods 0.000 description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 230000014759 maintenance of location Effects 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000002033 PVDF binder Substances 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 238000011056 performance test Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- -1 nanosilica Chemical compound 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material additive, a preparation method and application thereof, wherein the preparation method comprises the following steps: a) Heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution; b) Adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution; c) And grinding the dried precipitate, and burning the ground precipitate under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1). The lithium ion battery anode material additive prepared by the invention can effectively improve the multiplying power performance of the battery, increase the gram capacity exertion of the anode material and realize the stable circulation of the battery under high multiplying power. Meanwhile, the preparation method provided by the invention is simple and easy to operate and is easy to introduce into the existing battery system.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material additive, a preparation method and application thereof.
Background
At present, a method for improving the multiplying power performance of the ion battery is generally to add a composite conductive agent or perform coating treatment on a material layer. For adding the composite conductive agent, the effect is not obviously improved, the 0.5C cycle can hardly be carried out, and the current lithium ion battery requires high energy density, so that the content of active substances cannot be greatly reduced; meanwhile, the novel composite conductive agent is high in cost, and in the process of adding the single-wall carbon tube, the moisture of the pole piece is difficult to remove, and the serious gas production problem can be caused in the later stage, particularly in a lithium-rich battery system. Chinese patent CN108448089a discloses a solution for coating a material layer, and a nano-sized lithium-rich material is obtained by high-energy ball milling, so that the specific surface area is increased, and the rate performance is improved. However, the particles obtained by the method are difficult to homogenate in the amplifying production process, lithium battery slurry is difficult to obtain, and the particles are easy to crush in the rolling process and are separated from practice; meanwhile, the capacity of 0.1 g is 265mAh/g, the capacity of 0.2 g is 250mAh/g, the capacity of 0.5 g is 230mAh/g, the capacity of 1 g is 200mAh/g, the capacity of 2 g is 175mAh/g, the capacity of 4 g is 140mAh/g, and the gram capacity still needs to be improved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a lithium ion battery anode material additive, a preparation method and application thereof, and an electrochemical performance of a lithium ion battery prepared from an anode sheet added with the additive is better.
The invention provides a preparation method of a lithium ion battery anode material additive, which comprises the following steps:
a) Heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution;
b) Adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution;
c) Grinding the dried precipitate, and burning the dried precipitate under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (1)；
wherein 0< x <2,0< y <3.
Preferably, the mole ratio of the isopropyl titanate, the lithium oxalate, the aluminum nitrate, the nano silicon dioxide and the ammonium dihydrogen phosphate is 0.5-1.5: 2.5 to 3.5:0.5 to 1.5:0.5 to 1.5:4.5 to 5.5.
Preferably, in step a), the heating and mixing of isopropyl titanate, lithium oxalate, aluminum nitrate, ammonium dihydrogen phosphate and water comprises:
firstly, mixing isopropyl titanate, aluminum nitrate and part of water under stirring, then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest of water under stirring and mixing under heating;
The heating temperature is 75-85 ℃.
Preferably, the ratio of the total mass of the isopropyl titanate and the aluminum nitrate to the partial water is 0.5-2 g: 90-110 mL;
the ratio of the total mass of the lithium oxalate, the nano silicon dioxide and the ammonium dihydrogen phosphate to the residual water is 0.5-1.8 g: 40-60 mL.
Preferably, in the step B), the reagent for adjusting the pH value of the mixed solution is ammonia water;
the drying temperature is 115-125 ℃ and the drying time is 22-26 h.
Preferably, in the step C), the firing temperature is 880-920 ℃ and the firing time is 14-18 h;
after the firing, the method further comprises the following steps: naturally cooling to room temperature, and grinding again;
the grinding frequency of the secondary grinding is 480-520 Hz, and the time is 10-14 h.
The invention also provides the lithium ion battery anode material additive prepared by the preparation method.
The invention also provides a lithium ion battery positive plate which is prepared by uniformly mixing raw materials comprising a positive electrode material, an additive, conductive carbon black, single-walled carbon nanotubes and a binder and then coating the mixture on a current collector;
the positive electrode material comprises a lithium-rich manganese-based layered material, single-crystal lithium nickel manganese oxide, lithium iron phosphate or a high-voltage ternary material;
The additive is the additive of the positive electrode material of the lithium ion battery.
Preferably, the mass ratio of the positive electrode material to the additive is 92-98: 0.1 to 5;
the mass ratio of the positive electrode material to the conductive carbon black to the single-walled carbon nanotube to the binder is 92-98: 0.8 to 1.5:0.1 to 0.2:1.5.
the invention also provides a lithium ion battery which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the positive electrode is the positive plate of the lithium ion battery.
The invention provides a preparation method of a lithium ion battery anode material additive, which comprises the following steps that A) isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, monoammonium phosphate and water are heated and mixed to obtain a mixed solution; b) Adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution; c) And grinding the dried precipitate, and burning the ground precipitate under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1). The lithium ion battery anode material additive prepared by the invention can effectively improve the multiplying power performance of the battery, increase the gram capacity exertion of the anode material and realize the stable circulation of the battery under high multiplying power. Meanwhile, the preparation method provided by the invention is simple and easy to operate and is easy to introduce into the existing battery system.
Drawings
FIG. 1 shows the first efficiency and medium voltage after the battery pack of example 2 is formed into a battery pack;
fig. 2 is a graph showing the rate performance of button cells of example 2 and comparative example 1 of the present invention;
FIG. 3 is a cycle curve of the full cell of example 2 of the present invention at 0.5C rate;
FIG. 4 is a graph showing the capacity retention of the full cell of example 2 of the present invention cycled 325 times at 0.5C rate;
FIG. 5 is a 2000 SEM image of a positive electrode sheet of example 5 of the present invention;
FIG. 6 is a 1000-fold SEM image of a positive electrode sheet of example 5 of the present invention;
fig. 7 is a 10000-fold SEM image of the positive electrode sheet of example 6 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a lithium ion battery anode material additive, which comprises the following steps:
a) Heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution;
B) Adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution;
c) Grinding the dried precipitate, and burning the dried precipitate under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (1)；
wherein 0< x <2,0< y <3.
The invention firstly heats and mixes isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain mixed solution.
In certain embodiments of the invention, the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nanosilica, and ammonium dihydrogen phosphate is from 0.5 to 1.5:2.5 to 3.5:0.5 to 1.5:0.5 to 1.5:4.5 to 5.5. In certain embodiments, the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nanosilica, and ammonium dihydrogen phosphate is 1:3:1:1:5.
in certain embodiments of the invention, the water is deionized water.
In certain embodiments of the present invention, heat mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nanosilica, monoammonium phosphate, and water comprises:
firstly, mixing isopropyl titanate, aluminum nitrate and part of water under stirring, then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest of water under stirring and mixing under heating.
The stirring rotation speed of the stirring and mixing is not particularly limited, and stirring rotation speeds of stirring and mixing well known to those skilled in the art may be adopted.
In certain embodiments of the invention, the heating is at a temperature of 75 to 85 ℃. In certain embodiments, the temperature of the heating is 80 ℃.
In certain embodiments of the invention, the isopropyl titanate, aluminum nitrate, and a portion of the water are stirred and mixed for a period of time ranging from 0.5 to 1 hour. In some embodiments of the invention, lithium oxalate, nano-silica, ammonium dihydrogen phosphate and the rest of water are added and stirred and mixed for 0.5-1 h under the heating condition.
In certain embodiments of the invention, the ratio of the total mass of isopropyl titanate and aluminum nitrate to the amount of partial water is 0.5 to 2g: 90-110 mL. In certain embodiments, the ratio of the total mass of isopropyl titanate and aluminum nitrate to the amount of partial water is 1g:100mL.
In certain embodiments of the invention, the ratio of the total mass of lithium oxalate, nanosilica and ammonium dihydrogen phosphate to the amount of water remaining is 0.5 to 1.8g: 40-60 mL. In certain embodiments, the ratio of the total mass of lithium oxalate, nanosilica, and ammonium dihydrogen phosphate to the amount of water remaining is 1g:50mL.
And after the mixed solution is obtained, regulating the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution.
In certain embodiments of the invention, the agent that adjusts the pH of the mixed liquor is aqueous ammonia.
In the invention, the pH value of the mixed solution is adjusted to 9.6-10.0, so that precipitate is formed. In certain embodiments of the invention, the pH of the mixture is adjusted to 9.6.
The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
In certain embodiments of the invention, the filtration further comprises washing. The method of washing is not particularly limited, and washing methods well known to those skilled in the art may be employed.
In certain embodiments of the invention, the drying is at a temperature of 115-125 ℃ for a time of 22-26 hours. In certain embodiments of the invention, the drying is performed in a forced air drying oven.
After the drying is finished, grinding the dried precipitate, and burning the precipitate under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (1)；
wherein 0< x <2,0< y <3.
In certain embodiments of the invention, the milling process is ball milling. In some embodiments of the invention, the ball milling is performed at a rotational speed of 680-720 r/min for a period of 2.5-3.5 hours. In certain embodiments, the ball milling is performed at a rotational speed of 700r/min. In certain embodiments, the ball milling time is 3 hours.
In certain embodiments, the ball milling is performed in a zirconia ball milling tank. In certain embodiments of the invention, the particle size of the milled precipitate is 80 to 150nm.
In certain embodiments of the invention, the shielding gas is argon.
In certain embodiments of the invention, the firing temperature is 880-920 ℃ for 14-18 hours. In certain embodiments, the firing is performed in a tube furnace. In certain embodiments, the firing temperature is 900 ℃. In certain embodiments, the burn time is 16 hours.
In certain embodiments of the present invention, before firing under the condition of the shielding gas, the method further comprises: heating to firing temperature under the condition of protective gas.
In certain embodiments of the invention, the heating is at a rate of 2 to 4 ℃/min. In certain embodiments, the heating is at a rate of 3 ℃/min.
In some embodiments of the present invention, after the firing, the method further comprises: naturally cooling to room temperature, and grinding again.
In certain embodiments of the invention, the regrind is performed at a frequency of 480 to 520Hz for a period of 10 to 14 hours. In certain embodiments, the regrinding is performed in a sand mill. In certain embodiments, the regrind has a grind frequency of 500Hz. In certain embodiments, the time to regrind is 12 hours.
In certain embodiments of the invention, in formula (1), x=0.5 or 1, y=0.5, 1 or 2. Preferably, in formula (1), x=1 and y=1.
In certain embodiments of the present invention, the lithium ion battery positive electrode material additive having the general formula shown in formula (1) is a solid powder.
The invention also provides the lithium ion battery anode material additive prepared by the preparation method.
The invention also provides a lithium ion battery positive plate which is prepared by uniformly mixing raw materials comprising a positive electrode material, an additive, conductive carbon black, single-walled carbon nanotubes and a binder and then coating the mixture on a current collector;
the positive electrode material comprises a lithium-rich manganese-based layered material, single-crystal lithium nickel manganese oxide, lithium iron phosphate or a high-voltage ternary material;
the additive is the additive of the positive electrode material of the lithium ion battery.
In certain embodiments of the present invention, the lithium-rich manganese-based layered material is Li 1.44 Mn 0.544 Ni 0.136 Co 0.136 O 2 、Li 1.38 Mn 0.656 Ni 0.172 Co 0.171 O 2 Or Li (lithium) 1.348 Mn 0.66 Ni 0.17 Co 0.167 O 2 . In some embodiments of the present invention, the lithium-rich manganese-based layered material is from Ningbo materials institute of technology and engineering, academy of sciences, china.
In certain embodiments of the invention, the single crystal lithium nickel manganese oxide is single crystal 532 lithium nickel manganese oxide.
In certain embodiments of the invention, the binder is PVDF.
In certain embodiments of the present invention, the mass ratio of the positive electrode material to the additive is 92 to 98:0.1 to 5. In certain embodiments, the mass ratio of the positive electrode material to the additive is 97.5:0.1, 97.1:0.5, 96.6: 1. 95.1:2.5 or 92.6:5.
in certain embodiments of the present invention, the mass ratio of the positive electrode material, the conductive carbon black, the single-walled carbon nanotubes, and the binder is 92 to 98:0.8 to 1.5:0.1 to 0.2:1.5. in certain embodiments, the mass ratio of the positive electrode material, conductive carbon black, single-walled carbon nanotubes, and binder is 97.5:0.8:0.1:1.5, 97.1:0.8:0.1:1.5, 96.6:0.8:0.1:1.5, 95.1:0.8:0.1:1.5 or 92.6:0.8:0.1:1.5.
in certain embodiments of the invention, the current collector is aluminum foil. In certain embodiments, the aluminum foil has a thickness of 12 μm.
In certain embodiments of the invention, the lithium ion battery positive electrode sheet is prepared according to the following method:
a) Uniformly mixing a positive electrode material, an additive, conductive carbon black, single-walled carbon nanotubes and a binder to obtain positive electrode slurry;
b) And coating the positive electrode slurry on a current collector, and tabletting to obtain the positive electrode plate of the lithium ion battery.
In certain embodiments of the invention, the positive electrode slurry has a slurry viscosity of 4500mpa x s and a solids content of 63%.
The raw materials and the proportions adopted in the preparation method of the positive plate of the lithium ion battery are the same, and are not repeated here.
In certain embodiments of the invention, the thickness of the coating is 240 μm.
In certain embodiments of the invention, the lithium ion battery positive electrode sheet has a thickness of 200 μm.
The invention also provides a lithium ion battery which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is the positive plate of the lithium ion battery.
In certain embodiments of the present invention, a negative electrode sheet for a negative electrode is prepared according to the following method:
and coating the negative electrode slurry on a copper foil, and tabletting to obtain the negative electrode plate of the lithium ion battery.
In certain embodiments of the invention, the negative electrode slurry comprises silica, graphite, conductive carbon black, single-walled carbon nanotubes, and polyacrylic acid; the mass ratio of the silicon oxide, the conductive carbon black, the single-walled carbon nanotube and the polyacrylic acid is 51:44.8:1.04:0.06:3.1. in certain embodiments of the present invention, the gram capacity of silica and graphite in the negative electrode slurry is 1000mAh/g.
In certain embodiments of the present invention, the copper foil has a thickness of 6 μm.
In certain embodiments of the invention, the coating has a thickness of 125 μm.
In certain embodiments of the invention, the lithium ion battery negative electrode sheet has a thickness of 110 μm.
In certain embodiments of the invention, the membrane is a Xudi chemical membrane cellgard 2000.
In certain embodiments of the present invention, the electrolyte is national wav electrolyte 4750FB.
In certain embodiments of the invention, the positive electrode, the negative electrode, the separator, and the electrolyte are assembled into a pouch cell or a button cell.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The additive for the positive electrode material shown in the general formula (1) is applied to a liquid battery system, mainly utilizes the characteristic of a fast ion conductor of the additive to improve the positive electrode material with lower intrinsic ion conductivity, and utilizes the ion conduction characteristic of the additive and the cross-linking combination of the additive, an active substance in an electrode material and a conductive additive to improve ion transmission, so that the rate performance is greatly improved.
In order to further illustrate the present invention, the following examples are provided to describe in detail the positive electrode material additive for lithium ion batteries, its preparation method and application, but they should not be construed as limiting the scope of the present invention.
Example 1
The molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide and ammonium dihydrogen phosphate is 1:3:1:1:5;
1) Adding isopropyl titanate, aluminum nitrate and part of deionized water into a reaction container, and stirring for 0.8h; the ratio of the total mass of the isopropyl titanate and the aluminum nitrate to the partial water is 1g:100mL;
2) Then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest deionized water, stirring, heating to 80 ℃ and stirring for 0.5h to obtain a mixed solution; the ratio of the total mass of the lithium oxalate, the nano silicon dioxide and the ammonium dihydrogen phosphate to the residual water is 1g:50mL;
3) Adding ammonia water into the mixed solution to adjust the pH value to 9.6, forming precipitate, filtering and washing;
4) Drying in a forced air drying oven at 120 ℃ for 24 hours;
5) Ball milling for 3 hours at 700r/min in a zirconia ball milling tank, screening to obtain powder with the particle size of 80-150 nm, heating to 900 ℃ in a tube furnace at the speed of 3 ℃/min under the condition of argon, burning for 16 hours, and naturally cooling to room temperature;
6) And grinding for 12 hours in a sand mill at the frequency of 500Hz to obtain solid powder, namely the lithium ion battery anode material additive, which has the general formula shown in the formula (1), wherein x=1 and y=1.
Example 2
The lithium-rich manganese-based layered material LRM, an additive (the lithium ion battery positive electrode material additive prepared in example 1), conductive carbon black SP, single-wall carbon nano tube SWCNT and a binder PVDF are mixed according to the mass ratio of 97.5:0.1:0.8:0.1:1.5, uniformly mixing to obtain anode slurry; the LRM of the lithium-rich manganese-based layered material is Li 1.44 Mn 0.544 Ni 0.136 Co 0.136 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The slurry viscosity of the positive electrode slurry is 4500 Pa s, and the solid content is 63%;
coating the positive electrode slurry on aluminum foil with the thickness of 12 mu m, coating the aluminum foil with the thickness of 240 mu m, and tabletting to obtain a positive electrode sheet with the thickness of 200 mu m;
the preparation method comprises the following steps of mixing silicon oxide SiO, graphite, conductive carbon black SP, single-walled carbon nanotube SWCNT and polyacrylic acid PAA according to a mass ratio of 51:44.8:1.04:0.06:3.1, uniformly mixing to obtain negative electrode slurry; in the negative electrode slurry, the gram capacity of the silicon oxide and the graphite is 1000mAh/g;
coating the negative electrode slurry on copper foil with the thickness of 6 mu m, coating the copper foil with the thickness of 125 mu m, and tabletting to obtain a negative electrode plate with the thickness of 110 mu m;
and respectively assembling the negative plate, the positive plate, the Xudi formation diaphragm celgard2000 and electrolyte (national Hua appearance 4750 FB) into a soft package battery and a button battery, and standing the soft package battery at a high temperature of 45 ℃ for 24 hours.
After standing at high temperature, the first charge-discharge efficiency and medium voltage were recorded by the chemical composition operation, and the results are shown in fig. 1. Fig. 1 shows the first charge and discharge efficiency and medium voltage after the soft pack battery of example 2 is formed into a battery pack. In fig. 1, the discharge curves of 0.5C and 1C almost coincide with the discharge curve of 0.2C (fig. 1 includes the discharge curve and the charge curve, the discharge curves have the corresponding multiplying power of 0.2C,0.5C and 1C from top to bottom, the blue line has the corresponding multiplying power of 0.2C, the red line has the corresponding multiplying power of 0.5C and the green line has the corresponding multiplying power of 1C, the uppermost charge curve has the corresponding multiplying power of 0.2C, namely the blue line has the corresponding charging curves of 0.2C,0.5C and 1C, namely the black line has the corresponding charging curves of 0.5C and 1C), and the capacity ratio reaches 100%.
The specific steps of the chemical composition and the volume are as follows: standing the battery at a high temperature for t1, charging to U1 with a constant current of 0.02C, discharging to U2 with a constant current of 0.1C, charging to a constant current of 0.02C with a constant voltage of U2, discharging to U3 with a constant current of 0.1C for t2, decompressing, pumping and sealing, and completing the formation and the volume-dividing; t1 is 12h, U1 is 3.5V, U2 is 4.6V, U3 is 2.5V, and T2 is 3min.
The button cell prepared in example 2 was subjected to a multiplying power test, the test instrument was a LAND electrochemical tester, the test condition was room temperature, the constant current charge-discharge voltage was 2 to 4.6V, and the test result was shown in FIG. 2. Fig. 2 is a graph showing the rate performance of button cells of example 2 and comparative example 1 of the present invention. Wherein, add PW01 represents the rate performance curve of the button cell of example 2, and control represents the rate performance curve of the button cell of comparative example 1. As can be seen in FIG. 2, after the PW01 additive was added, the 0.1 g capacity was 300mAh/g, the 0.2 g capacity was 275mAh/g, the 1C g capacity was 240mAh/g, and the 2C g capacity was 220mAh/g.
In the embodiment, the LAND electrochemical tester is adopted to test the electrochemical performance of the full battery, the test condition is room temperature, the constant-current charge-discharge voltage is 2-4.6V, the cycle performance of the full battery is tested, the obtained cycle curve is shown in figure 3, and the obtained capacity retention rate is shown in figure 4.
Fig. 3 is a cycle curve of the full cell of example 2 of the present invention at 0.5C rate. Experiments show that the specific capacity of the button cell is 265mAh/g when the button cell is subjected to first discharge at the rate of 0.5C, and the specific capacity of the button cell is 250mAh/g after the button cell is subjected to cyclic charge and discharge for 250 times.
Fig. 4 is a graph showing the capacity retention rate of the full cell of example 2 of the present invention cycled 325 times at 0.5C rate. Experiments show that the capacity retention rate of the button cell after 325 times of circulation is 90% at the rate of 0.5C. After 300 times of cyclic charge and discharge, the specific discharge capacity is 245mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 90%.
Comparative example 1
The preparation method of the positive electrode slurry in example 2 was replaced with:
the lithium-rich manganese-based layered material LRM, the conductive carbon black SP and the binder PVDF are mixed according to the mass ratio of 8:1:1, uniformly mixing to obtain anode slurry; the LRM of the lithium-rich manganese-based layered material is Li 1.44 Mn 0.544 Ni 0.136 Co 0.136 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The paste viscosity of the positive electrode paste is 6000mpa x s, and the solid content is 63%;
the remaining steps were the same as those of example 2, to prepare a button cell. The button cell battery prepared in comparative example 1 was subjected to a rate test, and the results are shown in fig. 2. As can be seen from fig. 2, the gram capacity of the lithium-rich material is higher in the presence of the additive, and a stable cycle can be achieved at 10C, with comparative example 1 being up to 2C cycles only. Meanwhile, as can be seen from FIG. 2, in the case where no additive is added, the 0.1 g capacity is 280mAh/g, the 0.2 g capacity is 265mAh/g, the 1C g capacity is 216mAh/g, and the 2C g capacity is 220mAh/g.
Comparative example 2
The lithium-rich manganese-based layered material LRM, conductive carbon black SP, single-wall carbon nano tube SWCNT and binder PVDF are mixed according to the mass ratio of 97.5:0.8:0.1:1.5, uniformly mixing to obtain anode slurry; the LRM of the lithium-rich manganese-based layered material is Li 1.44 Mn 0.544 Ni 0.136 Co 0.136 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The slurry viscosity of the positive electrode slurry is 4500 Pa s, and the solid content is 63%;
coating the positive electrode slurry on aluminum foil with the thickness of 12 mu m, coating the aluminum foil with the thickness of 240 mu m, and tabletting to obtain a positive electrode sheet with the thickness of 200 mu m;
the preparation method comprises the following steps of mixing silicon oxide SiO, graphite, conductive carbon black SP, single-walled carbon nanotube SWCNT and polyacrylic acid PAA according to a mass ratio of 51:44.8:1.04:0.06:3.1, uniformly mixing to obtain negative electrode slurry; in the negative electrode slurry, the gram capacity of the silicon oxide and the graphite is 1000mAh/g;
coating the negative electrode slurry on copper foil with the thickness of 6 mu m, coating the copper foil with the thickness of 125 mu m, and tabletting to obtain a negative electrode plate with the thickness of 110 mu m;
and respectively assembling the negative plate, the positive plate, the Xudi formation diaphragm cellgard 2000 and electrolyte (national-Taihua capacity 4750FB and the lithium ion battery positive electrode material additive prepared in example 1, wherein the mass ratio of the additive to the lithium-rich manganese-based layered material LRM is 0.1:97.5) into a soft package battery and a button battery, and standing the soft package battery at a high temperature of 45 ℃ for 24 hours.
The button cell prepared in comparative example 2 was subjected to a rate test, and the experimental result showed that comparative example 2 was able to reach only 2C cycles at the highest.
The button cell prepared in comparative example 2 was subjected to a cycle performance test under the same conditions as in example 2, and the test showed that the specific capacity for the first discharge was 220mAh/g at a rate of 0.5C, and the specific capacity for the discharge was 160mAh/g after 250 cycles of charge and discharge. After 300 times of cyclic charge and discharge, the specific discharge capacity is 100mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 45.45%.
Example 3
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to be 97.1:0.5:0.8:0.1:1.5 (the additive amount of the additive in the positive electrode slurry is 0.5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 3 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 3 was subjected to a cycle performance test under the same conditions as in example 2, and the test showed that the specific capacity for the first discharge was 262mAh/g at a rate of 0.5C, and after 250 times of cycle charge and discharge, the specific capacity for the discharge was 250mAh/g. After 300 times of cyclic charge and discharge, the specific discharge capacity is 415mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 92%.
Example 4
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to 96.6:1:0.8:0.1:1.5 (the addition amount of the additive in the positive electrode slurry is 1 wt%) and uniformly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 4 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 4 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific discharge capacity of 268mAh/g for the first time at a rate of 0.5C and a specific discharge capacity of 252mAh/g after 250 times of cycle charge and discharge. After 300 times of cyclic charge and discharge, the specific discharge capacity is 247mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 94%.
Example 5
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to be 95.1:2.5:0.8:0.1:1.5 (the additive amount of the additive in the positive electrode slurry is 2.5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
Fig. 5 is a 2000-fold SEM image of the positive electrode sheet of example 5 of the present invention, and fig. 6 is a 1000-fold SEM image of the positive electrode sheet of example 5 of the present invention. As can be seen from fig. 5 and 6, the additive of the positive electrode material of the lithium ion battery is uniformly dispersed in the gaps of the lithium-rich manganese-based layered material, so that the conductive connection is enhanced, and the ion-conducting capability of the additive is higher, thereby improving the rate performance of the additive. Due to the action of Ti-O bonds, the surface/subsurface trace titanium element doping is beneficial to inhibiting the formation of disordered rock salt/spinel phases of lithium-rich materials, reducing interface lattice mismatch, and being beneficial to maintaining the stability of the structure and improving the rate capability and the cycle performance.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 5 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 5 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 270mAh/g for the first time at a rate of 0.5C and a specific capacity of 262mAh/g after 250 times of cyclic charge and discharge. After 300 times of cyclic charge and discharge, the specific discharge capacity is 250mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 94.7%.
Example 6
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to 92.6:5:0.8:0.1:1.5 (the addition amount of the additive in the positive electrode slurry is 5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
Fig. 7 is a 10000-fold SEM image of the positive electrode sheet of example 6 of the present invention. As can be seen from fig. 7, the additive of the positive electrode material of the lithium ion battery is uniformly dispersed in the gaps of the lithium-rich manganese-based layered material, so that the conductive connection is enhanced, and the ion conducting capability of the additive is stronger, thereby improving the rate performance of the additive.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 6 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 6 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 275mAh/g for the first time at a rate of 0.5C and a specific capacity of 250mAh/g after 250 times of cyclic charge and discharge. After 300 times of cyclic charge and discharge, the specific discharge capacity is 253mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 96.2%.
Example 7
The lithium-rich manganese-based layered material LRM in the positive electrode slurry of example 2 was replaced with lithium iron phosphate LFP, and the remaining steps were unchanged, and assembled into a pouch cell and a button cell, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 7 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in the example 7 is subjected to a cycle performance test under the same test conditions as those in the example 2, and experiments show that the button cell has a specific capacity of 145mAh/g for the first time under the 0.5C multiplying power and a specific capacity of 146mAh/g after being subjected to the cycle charge and discharge for 250 times. After 800 times of cyclic charge and discharge, the specific discharge capacity is 148mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 96.2%.
Example 8
The mass ratio of lithium iron phosphate LFP, additive (lithium ion battery positive electrode material additive prepared in example 1), conductive carbon black SP, single-walled carbon nanotube SWCNT and binder PVDF in example 7 was changed to 97.1:0.5:0.8:0.1:1.5 (the additive amount of the additive in the positive electrode slurry is 0.5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 8 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in the example 8 is subjected to a cycle performance test under the same test conditions as those in the example 2, and experiments show that the button cell has a specific discharge capacity of 150mAh/g for the first time at a rate of 0.5C and a specific discharge capacity of 143mAh/g after 250 times of cycle charge and discharge. After 800 times of cyclic charge and discharge, the specific discharge capacity is 142mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 97.1%.
Example 9
The mass ratio of lithium iron phosphate LFP, additive (lithium ion battery positive electrode material additive prepared in example 1), conductive carbon black SP, single-walled carbon nanotube SWCNT and binder PVDF in example 7 was changed to 96.6:1:0.8:0.1:1.5 (the addition amount of the additive in the positive electrode slurry is 1 wt%) and uniformly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 9 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 9 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 155mAh/g for the first time at a rate of 0.5C and a specific capacity of 148mAh/g after 250 times of cyclic charge and discharge. After 800 times of cyclic charge and discharge, the specific discharge capacity is 144mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 97.5%.
Example 10
The mass ratio of lithium iron phosphate LFP, additive (lithium ion battery positive electrode material additive prepared in example 1), conductive carbon black SP, single-walled carbon nanotube SWCNT and binder PVDF in example 7 was changed to 95.1:2.5:0.8:0.1:1.5 (the additive amount of the additive in the positive electrode slurry is 2.5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 10 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 10 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 157mAh/g for the first time at a rate of 0.5C and a specific capacity of 148mAh/g after 250 times of cyclic charge and discharge. After 800 times of cyclic charge and discharge, the specific discharge capacity is 146mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 97.6%.
Example 11
The mass ratio of the lithium iron phosphate LFP, the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 7 was changed to 92.6:5:0.8:0.1:1.5 (the addition amount of the additive in the positive electrode slurry is 5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 11 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 11 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 158mAh/g for the first time at a rate of 0.5C and a specific capacity of 152mAh/g after 250 times of cyclic charge and discharge. After 800 times of cyclic charge and discharge, the specific discharge capacity is 148mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 98.2%.
Example 12
The lithium-rich manganese-based layered material LRM in the positive electrode slurry of example 2 was replaced with single-crystal 532 lithium nickel manganese oxide (NCM 532), and the remaining steps were unchanged, and assembled into a soft-pack battery and a button cell, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 12 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 12 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 170mAh/g for the first time at a rate of 0.5C and a specific capacity of 160mAh/g after 250 times of cyclic charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 150mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 94.8%.
Example 13
The mass ratio of the single crystal 532 lithium nickel manganese oxide (NCM 532), the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 12 is changed to 97.1:0.5:0.8:0.1:1.5 (the additive amount of the additive in the positive electrode slurry is 0.5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 13 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 13 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 174mAh/g for the first time at a rate of 0.5C and a specific capacity of 165mAh/g after 250 times of cyclic charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 153mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 95.2%.
Example 14
The mass ratio of the single crystal 532 lithium nickel manganese oxide (NCM 532), the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 12 is changed to 96.6:1:0.8:0.1:1.5 (the addition amount of the additive in the positive electrode slurry is 1 wt%) and uniformly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 14 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 14 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 178mAh/g for the first time at a rate of 0.5C and a specific capacity of 168mAh/g after 250 times of cyclic charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 152mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 96.2%.
Example 15
The mass ratio of the single crystal 532 lithium nickel manganese oxide (NCM 532), the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 12 is changed to be 95.1:2.5:0.8:0.1:1.5 (the additive amount of the additive in the positive electrode slurry is 2.5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 15 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 15 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 182mAh/g for the first time at a rate of 0.5C and a specific capacity of 172mAh/g after 250 times of cyclic charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 158mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 96.6%.
Example 16
The mass ratio of the single crystal 532 lithium nickel manganese oxide (NCM 532), the additive (the lithium ion battery positive electrode material additive prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 12 is changed to 92.6:5:0.8:0.1:1.5 (the addition amount of the additive in the positive electrode slurry is 5 weight percent) and evenly mixing to obtain the positive electrode slurry;
the remaining steps were carried out in accordance with the procedure of example 2, and a pouch cell and a button cell were assembled, respectively.
The soft-packed battery was subjected to the formation composition operation according to the procedure of example 2 to record the first charge-discharge efficiency and medium voltage, and the experimental results show that the discharge curves of 0.5C,1C and 0.2C almost coincide, and the capacity ratio reaches 100%.
The button cell prepared in example 16 was subjected to a rate test under the same conditions as in example 2, and the experiment showed that the button cell could realize a stable cycle at 10C.
The button cell prepared in example 16 was subjected to a cycle performance test under the same test conditions as in example 2, and the experiment showed that the button cell had a specific capacity of 185mAh/g for the first time at a rate of 0.5C and a specific capacity of 168mAh/g after 250 times of cyclic charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 152mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 98.8%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the lithium ion battery anode material additive comprises the following steps:
A) Heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution;
b) Adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution;
c) Grinding the dried precipitate, and burning the dried precipitate under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (1)；
wherein 0< x <2,0< y <3.
2. The preparation method according to claim 1, wherein the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nano-silica and ammonium dihydrogen phosphate is 0.5-1.5: 2.5 to 3.5:0.5 to 1.5:0.5 to 1.5:4.5 to 5.5.
3. The method of claim 1, wherein in step a), the step of mixing isopropyl titanate, lithium oxalate, aluminum nitrate, ammonium dihydrogen phosphate, and water under heating comprises:
firstly, mixing isopropyl titanate, aluminum nitrate and part of water under stirring, then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest of water under stirring and mixing under heating;
the heating temperature is 75-85 ℃.
4. The method according to claim 3, wherein the ratio of the total mass of isopropyl titanate and aluminum nitrate to the amount of part of water is 0.5 to 2g: 90-110 mL;
The ratio of the total mass of the lithium oxalate, the nano silicon dioxide and the ammonium dihydrogen phosphate to the residual water is 0.5-1.8 g: 40-60 mL.
5. The method according to claim 1, wherein in the step B), the reagent for adjusting the pH of the mixed solution is aqueous ammonia;
the drying temperature is 115-125 ℃ and the drying time is 22-26 h.
6. The method according to claim 1, wherein in step C), the firing temperature is 880 to 920 ℃ for 14 to 18 hours;
after the firing, the method further comprises the following steps: naturally cooling to room temperature, and grinding again;
the grinding frequency of the secondary grinding is 480-520 Hz, and the time is 10-14 h.
7. The positive electrode material additive for lithium ion battery prepared by the preparation method of any one of claims 1 to 6.
8. The positive plate of the lithium ion battery is prepared by uniformly mixing raw materials comprising a positive electrode material, an additive, conductive carbon black, single-walled carbon nanotubes and a binder, and coating the mixture on a current collector;
the positive electrode material comprises a lithium-rich manganese-based layered material, single-crystal lithium nickel manganese oxide, lithium iron phosphate or a high-voltage ternary material;
the additive is the positive electrode material additive of the lithium ion battery of claim 7.
9. The positive plate of the lithium ion battery according to claim 8, wherein the mass ratio of the positive material to the additive is 92-98: 0.1 to 5;
the mass ratio of the positive electrode material to the conductive carbon black to the single-walled carbon nanotube to the binder is 92-98: 0.8 to 1.5:0.1 to 0.2:1.5.
10. a lithium ion battery, which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is the positive plate of the lithium ion battery of claim 8.
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| JP2008117543A (en) * | 2006-10-31 | 2008-05-22 | Ohara Inc | Lithium secondary battery, and electrode for lithium secondary battery |
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| WO2021091387A1 (en) * | 2019-11-07 | 2021-05-14 | Technische Universiteit Delft | Solid ionic conductive additive in electrodes for lithium-ion batteries using liquid electrolyte |
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| JP2008117543A (en) * | 2006-10-31 | 2008-05-22 | Ohara Inc | Lithium secondary battery, and electrode for lithium secondary battery |
| CN103715423A (en) * | 2014-01-06 | 2014-04-09 | 深圳市贝特瑞新能源材料股份有限公司 | LiNiCoAlO2 composite cathode material and preparation method thereof, and lithium ion battery |
| WO2021091387A1 (en) * | 2019-11-07 | 2021-05-14 | Technische Universiteit Delft | Solid ionic conductive additive in electrodes for lithium-ion batteries using liquid electrolyte |
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