CN114614010A - Silicon-containing negative electrode slurry of lithium ion battery and preparation method and application thereof - Google Patents
Silicon-containing negative electrode slurry of lithium ion battery and preparation method and application thereof Download PDFInfo
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- CN114614010A CN114614010A CN202210176705.3A CN202210176705A CN114614010A CN 114614010 A CN114614010 A CN 114614010A CN 202210176705 A CN202210176705 A CN 202210176705A CN 114614010 A CN114614010 A CN 114614010A
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- negative electrode
- silicon
- silane coupling
- coupling agent
- cellulose
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 47
- 239000010703 silicon Substances 0.000 title claims abstract description 47
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 45
- 229920002678 cellulose Polymers 0.000 claims abstract description 43
- 239000001913 cellulose Substances 0.000 claims abstract description 43
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000661 sodium alginate Substances 0.000 claims abstract description 38
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 38
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- 239000006258 conductive agent Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000011887 silicon containing negative electrode material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229920001046 Nanocellulose Polymers 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000003292 glue Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005056 compaction Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 claims description 4
- 229950005308 oxymethurea Drugs 0.000 claims description 4
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 claims description 2
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- -1 methacryloxy, mercapto Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 238000007599 discharging Methods 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 108010009736 Protein Hydrolysates Proteins 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910001006 Constantan Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 229940125753 fibrate Drugs 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003672 ureas Chemical group 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- 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
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The lithium ion battery silicon-containing negative electrode slurry comprises a silicon-containing negative electrode material, a conductive agent, a binder, a modification additive and a dispersing agent, wherein the modification additive is sodium alginate grafted silane coupling agent modified nano-cellulose. The addition of the modified additive provides sufficient buffer space for the volume expansion of the silicon-containing negative electrode material in the charging and discharging processes, improves the dispersibility of each component in the slurry, reduces the resistance of the pole piece, increases the wettability of the pole piece and the electrolyte, and plays a role in protecting the interface of the pole piece in the circulating process.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to silicon-containing negative electrode slurry of a lithium ion battery and a preparation method and application thereof.
Background
The performance of the cathode material, which is one of the important components of the lithium ion battery, greatly affects the overall performance of the lithium ion battery. At present, the commercial lithium ion battery cathode material is usually a graphitized carbon material, the specific capacity is low, the theoretical gram capacity is about 372mAh/g, and the high-rate charge-discharge performance is poor. The theoretical gram capacity of the silicon negative electrode is about 4200mAh/g, so that the adoption of the silicon-containing negative electrode material is a necessary trend for improving the gram capacity of the negative electrode at present. However, in the charging and discharging processes of the negative electrode added with the silicon-containing material, the phenomena of pulverization, falling off and the like are generated due to the overlarge volume expansion of silicon particles, so that the overall structure of the negative electrode is damaged, the cycle performance of the battery is poor, and even a safety problem is caused.
The research direction in the prior art is mostly focused on the improvement of a binder system and the addition of other additives, for example, CN109935832A discloses a silicon-based negative electrode binder of a lithium ion battery and a preparation method of a negative electrode plate using the binder, wherein the binder comprises a main binder and an auxiliary binder, the main binder is sodium alginate, the auxiliary binder comprises gelatin and at least one of sodium carboxymethylcellulose and styrene butadiene rubber, and the synergistic effect of multiple polymers improves the mechanical properties of a single binder to a certain extent. CN109314220A provides a negative electrode composition for a lithium ion battery, which comprises a silicon-based active material, a binder containing a carboxyl group, and a silane coupling agent. However, the increase of the amount of the polymer and the use of the silane coupling agent may more easily cause the agglomeration of inorganic particles, so that the internal resistance of the battery increases, which affects the battery performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides silicon-containing cathode slurry of a lithium ion battery, and a preparation method and application thereof. The modified additive is added into the negative electrode slurry, so that sufficient buffer space can be provided for the volume expansion of the silicon-containing negative electrode material in the charging and discharging processes, the dispersibility of each component in the slurry is improved, the resistance of a pole piece is reduced, the wettability of the pole piece and electrolyte is increased, and the effect of protecting the interface of the pole piece is achieved in the circulating process.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the slurry comprises a silicon-containing material, a conductive agent, a binder, a modified additive and a dispersing agent.
In the silicon-containing anode paste, the silicon-containing material may include SiOx、SiOxOne or more of a/C composite material and a Si/C composite material.
In the silicon-containing negative electrode slurry, the conductive agent is at least one of carbon black Super P, acetylene black, Ketjen black and graphene.
In the silicon-containing negative electrode slurry, the binder is an aqueous binder and includes one or more of a sodium carboxymethylcellulose (CMC) binder, a polyacrylic acid PAA, and a salt binder thereof.
In the silicon-containing negative electrode slurry, the modifying additive is sodium alginate grafted silane coupling agent modified nano-cellulose.
In the silicon-containing negative electrode slurry, the dispersant is water.
In the silicon-containing anode slurry, the following silicon-containing materials in parts by mass: conductive agent: adhesive: the mass ratio of the modifying additive is 85.0-96.0: 2.0-10.0: 1.0-5.0: 0.1-2.0, preferably, the mass ratio of the silicon-containing material: conductive agent: adhesive: the mass ratio of the modifying additive is 87.0-92.0: 4.0-7.0: 2.0-4.0: 0.1-1.0;
in the silicon-containing negative electrode slurry, the mass ratio of the solid material to the dispersant is 1: 0.6-1.5.
In the silicon-containing negative electrode paste, the silane coupling agent contains N, O elements, and the structural formula of the silane coupling agent can be Y (CH)2)nSiX3Wherein n is 0-3, X is a hydrolyzable group and comprises at least one of a chlorine group, an oxygen group and an acetoxy group, and Y is an organic functional group and comprises at least one of a vinyl group, an amino group, an epoxy group, a methacryloxy group, a mercapto group or a carbamide group.
In the silicon-containing negative electrode slurry, the morphology of the nanocellulose is preferably in a nanofiber state.
In the silicon-containing negative electrode slurry, the preparation method of the modification additive comprises the following steps:
(1) adding silane coupling agent into solvent, hydrolyzing under acidic condition,
(2) adding the nano-cellulose into the hydrolysate obtained in the step (1), reacting for 1-5 h at 40-70 ℃ to obtain the silane coupling agent modified nano-cellulose,
(3) and (3) carrying out grafting reaction on the silane coupling agent modified nanocellulose obtained in the step (2) and a sodium alginate solution to obtain sodium alginate grafted silane coupling agent modified nanocellulose.
In the invention, in the step (1), the solvent is a mixed solvent of ethanol and water, wherein the mass ratio of the ethanol to the water is 80-88: 10-15.
In the invention, in the step (1), the acidic condition can be realized by adding acid, preferably, the adding amount of the acid is controlled by adjusting the pH value to be 3-4. Preferably, the acid may be sulfuric acid, acetic acid and oxalic acid.
In the invention, in the step (1), the mass ratio of the silane coupling agent to the solvent is 0.1-5: 95-99.9.
In the invention, in the step (2), the mass ratio of the nano-cellulose to the silane coupling agent is 4-200: 1, preferably, the mass ratio of the nano-cellulose to the silane coupling agent is 50-150: 1;
in the invention, in the step (3), the adding amount of sodium alginate is 5-15% of the mass of the silane coupling agent modified nano-cellulose.
In the present invention, in the step (3), the grafting agent is an N-methylol compound, preferably any one or more of dimethylol urea, trimethylol melamine, dimethylol ethylene urea and dimethylol dihydroxy ethylene urea,
in the invention, in the step (3), the addition amount of the grafting agent is 5-12% of the mass of the silane coupling agent modified nano-cellulose.
In the invention, a catalyst is also added in the grafting reaction in the step (3), and the catalyst is any one or more of magnesium chloride, zinc nitrate and basic aluminum chloride.
In the invention, the adding amount of the catalyst in the step (3) is 1-2% of the mass of the silane coupling agent modified nano-cellulose.
In the invention, the reaction temperature of the step (3) is 30-60 ℃, and the reaction time is 0.5-2 h.
And drying the prepared sodium alginate grafted silane coupling agent modified nano-cellulose at 60-150 ℃.
The sodium alginate grafted silane coupling agent modified nano-cellulose provided by the invention is used as a modification additive to be added into a silicon-containing cathode homogenization process, and has the following advantages: (1) sodium alginate is used as a common adhesive, has poor mechanical stability, and after being grafted with nano-cellulose, the mechanical stability of the sodium alginate is improved, and the carboxyl content of the sodium alginate is higher, so that the hydrophilicity of the nano-cellulose is improved, and the sodium alginate can be used as a reinforcing agent of the original adhesive of the sizing agent to a certain extent, and the adhesive property of the sizing agent is ensured; (2) the addition of the modified additive in a proper proportion can enhance the film-forming property of the slurry, the nanofiber structure can provide enough buffer space for the volume expansion of the silicon-containing negative electrode material in the charging and discharging processes, the uniformity of each component in the slurry is improved, and the agglomeration of inorganic particles caused by simply increasing the dosage of the polymer binder is avoided, so that the internal resistance of the material is reduced; (3) during the charging and discharging process of the battery, LiPF in the electrolyte can be caused by the existence of trace water6The modified nanocellulose can react with HF by adopting silane coupling agent containing N, O element, so as to protect the positive and negative electrode plates from being corroded.
The invention also provides a preparation method of the cathode slurry, which comprises the following steps:
step S1, adding the binder and the modified additive into the dispersant, and stirring into a glue solution, wherein the stirring speed is preferably 300-500 r/min, and the stirring time is preferably 200-240 min;
and step S2, adding a conductive agent and a silicon-containing negative electrode material into the glue solution obtained in the step S1, and stirring to obtain negative electrode slurry, wherein preferably, the stirring revolution speed is 1800-2500 r/min, and the stirring time is 5-20 min.
The invention also provides application of the negative electrode slurry, and the negative electrode slurry can be used for preparing a negative electrode plate of a lithium ion battery.
The negative pole piece of the lithium ion battery is prepared by adopting the silicon-containing negative pole slurry.
Further, the preparation method of the negative pole piece comprises the following steps:
step A1, uniformly coating the negative electrode slurry on a copper foil, wherein the coating thickness is 50-250 μm, and preferably 100-150 μm;
step A2, drying the current collector coated with the negative electrode slurry under a vacuum condition, wherein the temperature is 120-180 ℃, and the drying time is 4-12 h;
step A3, rolling the dried pole piece, wherein the compaction density of the pole piece is 1.0-1.5 g/cm3。
The invention also provides a lithium ion battery which comprises the negative pole piece, wherein the negative pole piece is the negative pole piece.
The invention has the following positive effects:
the silicon-containing negative electrode slurry of the lithium ion battery adopts sodium alginate grafted silane coupling agent modified nano-cellulose as a modification additive. Sufficient buffer space is provided for the volume expansion of the silicon-containing material in the charging and discharging process, the mechanical stability of the binder in the slurry is improved, the dispersibility of each component in the slurry is improved, the internal resistance of the material is reduced, and the silane coupling agent containing N, O elements can play a role in protecting the interface of the pole piece in the circulating process. On the other hand, the sodium alginate grafted silane coupling agent modified nanocellulose with large length-diameter ratio can improve the wettability of the electrolyte to the pole piece, so that the contact with the electrolyte is more sufficient, and the electronic conductivity and the lithium ion transmission capability of the pole piece are improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The raw material sources are as follows: nanocellulose (nanocellulose CNF, wuhan constantan biomedical limited).
Example 1
By means of H2SO4Adjusting the pH value of an ethanol solution to 3.5, adding a certain amount of silane coupling agent KH-A115 into the ethanol solution, stirring the mixture to fully hydrolyze the mixture to obtain KH-A115 hydrolysate, wherein the mass ratio of KH-A115 to ethanol to water is 0.1 to 88 to 11.9 percent, adding nano-cellulose into the KH-A115 hydrolysate, and heating the mixture at 40 ℃ for 5 hours to obtain KH-A115 modified nano-cellulose, wherein the mass ratio of nano-cellulose to KH-A115 is 4 to 1;
adding KH-A115 modified nanocellulose into a sodium alginate solution for a grafting reaction, wherein the adding amount of the sodium alginate is 5% of the mass of the silane coupling agent modified nanocellulose, then adding dimethylol urea which is 5% of the mass of the aminosilane modified nanocellulose and magnesium chloride which is 1% of the mass of the KH-A115 modified nanocellulose, stirring for 2h at 30 ℃ to prepare the sodium alginate grafted KH-A115 modified nanocellulose, and then drying at 60 ℃.
Adding CMC binder and sodium alginate grafted KH-A115 modified nano-cellulose into dispersant water, stirring to obtain a glue solution, wherein the stirring speed is 300r/min, the stirring time is 240min, adding conductive agent Super P and silicon-containing negative electrode material into the glue solution, and stirring to obtain negative electrode slurry, wherein the silicon-containing material: conductive agent: adhesive: the mass ratio of the modifying additive is 89.9:5.0:5.0:0.1, the mass ratio of the solid material to the water is 1:0.6, the stirring revolution speed is 1800r/min, and the stirring time is 15 min.
The silicon-containing cathode material is SiOx(silica, Sichuan super Van.).
Uniformly coating the negative electrode slurry on a copper foil with the coating thickness of 50 mu m, drying the current collector coated with the negative electrode slurry under the vacuum condition at the temperature of 120 ℃ for 12h, and dryingRolling the dried pole piece, wherein the compaction density of the pole piece is 1.0-1.5 g/cm3。
The pole piece is used for manufacturing a CR2032 button cell.
Example 2
Adjusting the pH value of an ethanol solution to 4 by adopting acetic acid, adding a certain amount of silane coupling agent KH550 into the ethanol solution, stirring the mixture to fully hydrolyze the mixture to obtain KH550 hydrolysate, wherein the mass ratio of KH550 to ethanol to water is 5 to 80 to 15 percent, adding nano-cellulose into the KH550 hydrolysate, and heating the mixture at 70 ℃ for 1 hour to obtain KH550 modified nano-cellulose, wherein the mass ratio of the nano-cellulose to KH550 is 200: 1;
adding KH550 modified nanocellulose into a sodium alginate solution for a grafting reaction, wherein the adding amount of sodium alginate is 15% of the mass of the nanocellulose modified by a silane coupling agent, adding trimethylolmelamine accounting for 12% of the mass of the KH550 modified nanocellulose and zinc nitrate accounting for 2% of the mass of the KH550 modified nanocellulose, stirring for 0.5h at 60 ℃ to prepare the sodium alginate grafted KH550 modified nanocellulose, and drying at 150 ℃.
Adding polyacrylic acid (PAA) as a binder and sodium alginate grafted KH550 modified nano-cellulose into dispersant water, stirring to form a glue solution, wherein the stirring speed is 500r/min, the stirring time is 200min, adding acetylene black as a conductive agent and a silicon-containing negative electrode material into the glue solution, and stirring to obtain a negative electrode slurry, wherein the silicon-containing material: conductive agent: adhesive: the mass ratio of the modifying additive is 85.0:10.0:3.0:2.0, the mass ratio of the solid material to the water is 1:1.5, the stirring revolution speed is 2500r/min, and the stirring time is 5 min.
The silicon-containing cathode material is SiO coated on the surfacexGraphite (fibrate S420-2A) was blended.
Uniformly coating the negative electrode slurry on a copper foil, wherein the coating thickness is 250 mu m, drying the current collector coated with the negative electrode slurry under a vacuum condition, the temperature is 180 ℃, the drying time is 8 hours, rolling the dried pole piece, and the compaction density of the pole piece is 1.0-1.5 g/cm3。
The pole piece is used for manufacturing a CR2032 button cell.
Example 3
Adjusting the pH value of an ethanol solution to 3 by using oxalic acid, adding a certain amount of silane coupling agent KH792 into the ethanol solution, stirring the mixture to fully hydrolyze the mixture to obtain KH792 hydrolysate, wherein the mass ratio of KH792 to ethanol to water is 3%: 87%: 10%, adding nanocellulose into the KH792 hydrolysate, and heating the mixture at 55 ℃ for 3 hours to obtain KH792 modified nanocellulose, wherein the mass ratio of the nanocellulose to KH792 is 100: 1;
adding KH792 modified nanocellulose into a sodium alginate solution for a grafting reaction, wherein the adding amount of sodium alginate is 8% of the mass of silane coupling agent modified nanocellulose, adding dimethylol ethylene urea accounting for 8% of the mass of KH792 modified nanocellulose and basic aluminum chloride accounting for 1.5% of the mass of KH792 modified nanocellulose, stirring for 1h at 50 ℃ to prepare sodium alginate grafted KH792 modified nanocellulose, and drying at 100 ℃.
Adding sodium polyacrylate serving as a binder and sodium alginate grafted KH792 modified nanocellulose into dispersant water, stirring to form glue solution, wherein the stirring speed is 400r/min, the stirring time is 220min, adding Ketjen black serving as a conductive agent and a silicon-containing negative electrode material into the glue solution, and stirring to obtain negative electrode slurry, wherein the silicon-containing material: conductive agent: adhesive: the mass ratio of the modifying additive is 96.0:2.0:1.0:1.0, the mass ratio of the solid material to the water is 1:1.0, the stirring revolution speed is 2000r/min, and the stirring time is 20 min.
The silicon-containing negative electrode material is nano silicon blended graphite (apres ASG450 Ec).
Uniformly coating the negative electrode slurry on a copper foil, wherein the coating thickness is 100 mu m, drying the current collector coated with the negative electrode slurry under a vacuum condition, the temperature is 150 ℃, the drying time is 4h, rolling the dried pole piece, and the compaction density of the pole piece is 1.0-1.5 g/cm3。
The pole piece is used for manufacturing a CR2032 button cell.
Comparative example 1
Adding CMC binder into dispersant water, stirring into a glue solution at the stirring speed of 300r/min for 240min, adding a conductive agent Super P and a silicon-containing negative electrode material into the glue solution, and stirring to obtain a negative electrode slurry, wherein the silicon-containing material: conductive agent: the mass ratio of the binder is 90.0:5.0:5.0, the mass ratio of the solid material to the water is 1:0.6, the stirring revolution speed is 1800r/min, and the stirring time is 15 min.
The silicon-containing cathode material is SiOx(silica, Sichuan ultra Van.).
Uniformly coating the negative electrode slurry on a copper foil with the coating thickness of 50 mu m, drying the current collector coated with the negative electrode slurry under the vacuum condition at the temperature of 120 ℃ for 12h, rolling the dried pole piece, wherein the compaction density of the pole piece is 1.0-1.5 g/cm3。
The pole piece is used for manufacturing a CR2032 button cell.
Comparative example 2
By means of H2SO4Adjusting the pH value of an ethanol solution to 3.5, adding a certain amount of silane coupling agent KH-A115 into the ethanol solution, stirring the mixture to fully hydrolyze the mixture to obtain KH-A115 hydrolysate, wherein the mass ratio of KH-A115 to ethanol to water is 0.1 percent to 88 percent to 11.9 percent, adding nano-cellulose into the KH-A115 hydrolysate, and heating the mixture at 40 ℃ for 5 hours to obtain KH-A115 modified nano-cellulose, wherein the mass ratio of nano-cellulose to KH-A115 is 4: 1.
Adding a CMC binder and KH-A115 modified nano-cellulose into dispersant water, stirring to obtain a glue solution, wherein the stirring speed is 300r/min, the stirring time is 240min, adding a conductive agent Super P and a silicon-containing negative electrode material into the glue solution, and stirring to obtain a negative electrode slurry, wherein the silicon-containing material: conductive agent: adhesive: the mass ratio of the KH-A115 modified nano-cellulose is 89.9:5.0:5.0:0.1, the mass ratio of the solid material to the water is 1:0.6, the stirring revolution speed is 1800r/min, and the stirring time is 15 min.
The silicon-containing cathode material is SiOx(silica, Sichuan super Van.).
Uniformly coating the negative electrode slurry on a copper foil with the coating thickness of 50 mu m, drying the current collector coated with the negative electrode slurry under the vacuum condition at the temperature of 120 ℃ for 12h, rolling the dried pole piece, wherein the compaction density of the pole piece is 1.0-1.5 g/cm3。
The pole piece is used for manufacturing a CR2032 button cell.
Comparative example 3
Adding the nano-cellulose into a sodium alginate solution for grafting reaction, wherein the adding amount of the sodium alginate is 5% of the mass of the nano-cellulose, then adding dimethylol urea accounting for 5% of the mass of the nano-cellulose and magnesium chloride accounting for 1% of the mass of the nano-cellulose, stirring for 2h at 30 ℃ to prepare the sodium alginate grafted nano-cellulose, and then drying at 60 ℃.
Adding CMC binder and sodium alginate grafted nano-cellulose into dispersant water, stirring to obtain a glue solution, wherein the stirring speed is 300r/min, the stirring time is 240min, adding conductive agent Super P and silicon-containing negative electrode material into the glue solution, and stirring to obtain negative electrode slurry, wherein the silicon-containing material: conductive agent: adhesive: the mass ratio of the sodium alginate grafted nano cellulose is 89.9:5.0:5.0:0.1, the mass ratio of the solid material to the water is 1:0.6, the stirring revolution speed is 1800r/min, and the stirring time is 15 min.
The silicon-containing cathode material is SiOx(silica, Sichuan super Van.).
Uniformly coating the negative electrode slurry on a copper foil with the coating thickness of 50 mu m, drying the current collector coated with the negative electrode slurry under a vacuum condition at the temperature of 120 ℃ for 12 hours, rolling the dried pole piece, wherein the compaction density of the pole piece is 1.0-1.5 g/cm3。
The pole piece is used for manufacturing a CR2032 button cell.
Preparation of CR2032 button cell:
in an environment with the humidity lower than 5%, cutting the rolled pole piece into a round pole piece with the diameter of 14mm by using a cutting machine, putting the round pole piece into a glove box in an argon atmosphere, assembling the battery in the glove box according to the sequence of 'negative pole shell-shrapnel-gasket-lithium piece-electrolyte-diaphragm-electrolyte-pole piece-positive pole shell', then compacting the battery by using a sealing machine, and absorbing the redundant electrolyte by using dust-free paper.
The CR2032 batteries obtained in examples 1 to 3 and comparative examples 1 to 3 were allowed to stand for 6 hours, and then subjected to a charge-discharge capacity test and a charge-discharge cycle test at a temperature of 25. + -. 1 ℃ on a Xinwei charge-discharge test cabinet, respectively, and the test results are shown in Table 1.
Testing the charge-discharge capacity and the coulombic efficiency of the first circle: discharging at 0.05C multiplying power, charging at 0.1C multiplying power, the cut-off voltage range is 0.01-1.5V, and the first turn coulombic efficiency is that the charging capacity/the discharging capacity is multiplied by 100 percent.
And (3) testing charge and discharge cycles: discharging at 0.05C multiplying power, charging at 0.1C multiplying power, and cut-off voltage range of 0.01-1.5V, and taking the ratio of the charging capacity of 100 times of cycle to the charging capacity of the first time as the capacity retention rate of 100 times of charge-discharge cycle.
The negative electrode pieces obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to a pole piece peel strength test and a pole piece resistance test, and the test results are shown in table 2.
Testing the peel strength of the pole piece: the pole piece was cut into strips of 15mm width, the coated side of the pole piece was fixed to a stainless steel plate with 3M9448A double-sided tape, rolled 10 times with a 2kg standard roller and then peeled 180 degrees with a tensile tester at a speed of 50 mm/min.
Testing the resistance of the pole piece: and testing the resistance of the pole piece by using a pole piece resistance tester, wherein the testing pressure is 0.4 t.
TABLE 1
TABLE 2
| Numbering | Pole piece peel strength (N/m) | Pole piece resistance (omega) |
| Example 1 | 6.03 | 0.152 |
| Example 2 | 5.49 | 0.087 |
| Example 3 | 5.99 | 0.083 |
| Comparative example 1 | 2.52 | 4.080 |
| Comparative example 2 | 3.41 | 2.335 |
| Comparative example 3 | 4.28 | 1.008 |
As can be seen from the results of tables 1 and 2, the above-described embodiment of the present invention achieves the following technical effects: according to the preparation method of the lithium ion battery cathode slurry and the pole piece thereof, provided by the invention, the appropriate proportion of the modified additive, namely the sodium alginate grafted silane coupling agent modified nano-cellulose is added in the step of homogenizing, so that the mechanical stability of the binder in the slurry is improved, and the dispersibility of each component in the slurry is improved. The negative pole piece has higher peel strength and lower pole piece resistance under the coating thickness and the compaction density provided by the invention, and the sodium alginate grafted silane coupling agent modified nano-cellulose with large length-diameter ratio can improve the wettability of the electrolyte to the pole piece, so that the negative pole piece is more fully contacted with the electrolyte, and the electronic conductivity and the lithium ion transmission capability of the pole piece are improved. In addition, the special structure of the modified additive provides enough buffer space for the volume expansion of the silicon-containing material in the charging and discharging process, the silane coupling agent containing N, O element can play a role in protecting the interface of the pole piece in the circulating process, and the prepared battery has the characteristics of high coulomb efficiency of the first circle, long circulating life and the like.
It should be understood by those skilled in the art that the above embodiments are only preferred embodiments of the present invention, and any changes, equivalents and modifications made without departing from the spirit and scope of the present application should be included in the protection scope of the present invention.
Claims (10)
1. The silicon-containing negative electrode slurry of the lithium ion battery is characterized by comprising a silicon-containing material, a conductive agent, a binder, a modified additive and a dispersing agent.
2. The silicon-containing anode slurry according to claim 1, wherein the silicon-containing material comprises SiOx、SiOxOne or more of a/C composite material and a Si/C composite material;
preferably, the conductive agent is one or more of carbon black Super P, acetylene black, Ketjen black and graphene;
preferably, the binder is an aqueous binder, and comprises one or more of sodium carboxymethylcellulose binder, polyacrylic acid and salts thereof;
preferably, the modified additive is sodium alginate grafted silane coupling agent modified nano-cellulose;
preferably, the silane coupling agent contains N, O elements and can be represented by the formula Y (CH)2)nSiX3Wherein n is 0-3, X is a hydrolyzable group including at least one of a chloro group, an oxy group and an acetoxy group, Y is an organic functional group including a vinyl group, an amino group, an epoxy group, a carboxyl group,at least one of methacryloxy, mercapto or ureido;
preferably, the morphology of the nanocellulose is preferably in a nanofibrous shape;
preferably, the dispersant is water.
3. The silicon-containing anode slurry according to claim 1 or 2, wherein the silicon-containing material: conductive agent: adhesive: the mass ratio of the modifying additive is 85.0-96.0: 2.0-10.0: 1.0-5.0: 0.1-2.0, preferably, the mass ratio of the silicon-containing material: conductive agent: adhesive: the mass ratio of the modifying additive is 87.0-92.0: 4.0-7.0: 2.0-4.0: 0.1-1.0;
preferably, the mass ratio of the total mass of the silicon-containing material, the conductive agent, the binder and the modifying additive to the dispersing agent is 1: 0.6-1.5.
4. The silicon-containing anode slurry according to any one of claims 1 to 3, wherein the preparation method of the modification additive comprises the steps of:
(1) adding silane coupling agent into solvent, hydrolyzing under acidic condition,
(2) adding the nano-cellulose into the hydrolysate obtained in the step (1), reacting for 1-5 h at 40-70 ℃ to obtain the silane coupling agent modified nano-cellulose,
(3) and (3) carrying out grafting reaction on the silane coupling agent modified nanocellulose obtained in the step (2) and a sodium alginate solution to obtain sodium alginate grafted silane coupling agent modified nanocellulose.
5. The slurry according to claim 4, characterized in that in the step (1), the solvent is a mixed solvent of ethanol and water, wherein the mass ratio of ethanol to water is 80-88: 10-15;
preferably, in the step (1), the acidic condition can be realized by adding acid, and preferably, the adding amount of the acid is based on the adjustment of the PH value to 3-4;
preferably, the acid may be sulfuric acid, acetic acid and oxalic acid;
preferably, in the step (1), the mass ratio of the silane coupling agent to the solvent is 0.1-5: 95-99.9.
6. The slurry according to claim 4 or 5, wherein in the step (2), the mass ratio of the nano-cellulose to the silane coupling agent is 4-200: 1, preferably the mass ratio of the nano-cellulose to the silane coupling agent is 50-150: 1;
preferably, in the step (3), the adding amount of the sodium alginate is 5-15% of the mass of the silane coupling agent modified nano-cellulose.
7. The slurry according to claim 4, wherein in the step (3), the grafting agent is N-methylol compound, preferably any one or more of dimethylol urea, trimethylol melamine, dimethylol ethylene urea and dimethylol dihydroxy ethylene urea;
preferably, in the step (3), the addition amount of the grafting agent is 5-12% of the mass of the silane coupling agent modified nanocellulose;
preferably, a catalyst is also added in the grafting reaction in the step (3), and the catalyst is any one or more of magnesium chloride, zinc nitrate and basic aluminum chloride;
preferably, the adding amount of the catalyst in the step (3) is 1-2% of the mass of the silane coupling agent modified nano-cellulose;
preferably, the reaction temperature in the step (3) is 30-60 ℃, and the reaction time is 0.5-2 h;
preferably, the prepared sodium alginate grafted silane coupling agent modified nano-cellulose is dried at the temperature of 60-150 ℃.
8. A method for preparing the negative electrode slurry according to any one of claims 1 to 7, comprising the steps of:
step S1, adding the binder and the modified additive into the dispersant, and stirring into a glue solution, wherein the stirring speed is preferably 300-500 r/min, and the stirring time is preferably 200-240 min;
and step S2, adding a conductive agent and a silicon-containing negative electrode material into the glue solution obtained in the step S1, and stirring to obtain negative electrode slurry, wherein preferably, the stirring revolution speed is 1800-2500 r/min, and the stirring time is 5-20 min.
9. Use of the paste according to any one of claims 1 to 7 or of the negative paste prepared by the preparation method according to claim 8 for preparing a negative electrode sheet of a lithium ion battery;
preferably, the preparation method of the negative electrode plate comprises the following steps:
step A1, uniformly coating the negative electrode slurry on a copper foil, wherein the coating thickness is 50-250 μm, and preferably 100-150 μm;
step A2, drying the current collector coated with the negative electrode slurry under a vacuum condition, wherein the temperature is 120-180 ℃, and the drying time is 4-12 h;
step A3, rolling the dried pole piece, wherein the compaction density of the pole piece is 1.0-1.5 g/cm3。
10. A lithium ion battery comprising a negative electrode tab, wherein the negative electrode tab is the negative electrode tab of claim 9.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140050975A1 (en) * | 2012-08-20 | 2014-02-20 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and negative electrode and rechargeable lithium battery including same |
| CN103633298A (en) * | 2012-08-28 | 2014-03-12 | 华为技术有限公司 | Lithium ion battery silicon negative electrode sheet and preparation method thereof, and lithium ion battery |
| CN103762367A (en) * | 2014-01-21 | 2014-04-30 | 厦门大学 | Method for preparing silicon-based anode material adhesive of lithium ion battery |
| WO2015098050A1 (en) * | 2013-12-26 | 2015-07-02 | 日本ゼオン株式会社 | Slurry composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| CN106920968A (en) * | 2015-12-25 | 2017-07-04 | 深圳市比克动力电池有限公司 | Lithium ion battery negative batch mixing, negative pole and lithium ion battery |
| WO2018077937A1 (en) * | 2016-10-28 | 2018-05-03 | Volkswagen Aktiengesellschaft | New binder systems for silicon-containing composite electrodes for lithium ion batteries |
| CN108232129A (en) * | 2016-12-21 | 2018-06-29 | 深圳市比克动力电池有限公司 | Lithium ion battery negative material, negative plate and lithium ion battery |
| CN108987753A (en) * | 2018-07-23 | 2018-12-11 | 芜湖彰鸿工程技术有限公司 | A kind of new energy bonder for lithium ion batteries and its application |
| CN109301248A (en) * | 2017-07-24 | 2019-02-01 | 南方科技大学 | Battery cathode sheet and preparation method thereof and lithium ion battery |
| CN109935832A (en) * | 2018-11-21 | 2019-06-25 | 万向一二三股份公司 | A kind of lithium ion battery silicon substrate negative electrode binder and the cathode piece preparation method using the binder |
| CN110247017A (en) * | 2019-06-13 | 2019-09-17 | 浙江吉利控股集团有限公司 | For the binder of lithium ion battery silicon substrate cathode, lithium ion battery silicon substrate cathode and preparation method thereof, lithium ion battery |
| US20190312258A1 (en) * | 2016-11-25 | 2019-10-10 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Negative electrode of nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN113224284A (en) * | 2021-04-26 | 2021-08-06 | 东莞市创明电池技术有限公司 | Lithium ion battery cathode and preparation method thereof, and lithium ion battery |
-
2022
- 2022-02-25 CN CN202210176705.3A patent/CN114614010B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140050975A1 (en) * | 2012-08-20 | 2014-02-20 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and negative electrode and rechargeable lithium battery including same |
| CN103633298A (en) * | 2012-08-28 | 2014-03-12 | 华为技术有限公司 | Lithium ion battery silicon negative electrode sheet and preparation method thereof, and lithium ion battery |
| WO2015098050A1 (en) * | 2013-12-26 | 2015-07-02 | 日本ゼオン株式会社 | Slurry composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| CN103762367A (en) * | 2014-01-21 | 2014-04-30 | 厦门大学 | Method for preparing silicon-based anode material adhesive of lithium ion battery |
| CN106920968A (en) * | 2015-12-25 | 2017-07-04 | 深圳市比克动力电池有限公司 | Lithium ion battery negative batch mixing, negative pole and lithium ion battery |
| WO2018077937A1 (en) * | 2016-10-28 | 2018-05-03 | Volkswagen Aktiengesellschaft | New binder systems for silicon-containing composite electrodes for lithium ion batteries |
| US20190312258A1 (en) * | 2016-11-25 | 2019-10-10 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Negative electrode of nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN108232129A (en) * | 2016-12-21 | 2018-06-29 | 深圳市比克动力电池有限公司 | Lithium ion battery negative material, negative plate and lithium ion battery |
| CN109301248A (en) * | 2017-07-24 | 2019-02-01 | 南方科技大学 | Battery cathode sheet and preparation method thereof and lithium ion battery |
| CN108987753A (en) * | 2018-07-23 | 2018-12-11 | 芜湖彰鸿工程技术有限公司 | A kind of new energy bonder for lithium ion batteries and its application |
| CN109935832A (en) * | 2018-11-21 | 2019-06-25 | 万向一二三股份公司 | A kind of lithium ion battery silicon substrate negative electrode binder and the cathode piece preparation method using the binder |
| CN110247017A (en) * | 2019-06-13 | 2019-09-17 | 浙江吉利控股集团有限公司 | For the binder of lithium ion battery silicon substrate cathode, lithium ion battery silicon substrate cathode and preparation method thereof, lithium ion battery |
| CN113224284A (en) * | 2021-04-26 | 2021-08-06 | 东莞市创明电池技术有限公司 | Lithium ion battery cathode and preparation method thereof, and lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| XIE, WG ET AL.: "Investigation on elecctrolyte-immersed properties of lithium-io battery cellulose separator through multi-scale method", JOURNAL OF POWER SOURCES, vol. 417, pages 150 - 158, XP085614642, DOI: 10.1016/j.jpowsour.2019.02.002 * |
| 冯小芳;李明齐;: "硅氧烷用量对SiO_x@C纳米复合材料储锂性能影响", 电源技术, no. 12, pages 2313 - 2316 * |
| 郑颖;杨军;陶亮;努丽燕娜;王久林;: "锂离子电池用多孔硅/石墨/碳复合负极材料的研究", 无机化学学报, no. 11, pages 1882 - 1886 * |
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