CN110534699A - A kind of preparation method of anode plate for lithium ionic cell - Google Patents
A kind of preparation method of anode plate for lithium ionic cell Download PDFInfo
- Publication number
- CN110534699A CN110534699A CN201910776951.0A CN201910776951A CN110534699A CN 110534699 A CN110534699 A CN 110534699A CN 201910776951 A CN201910776951 A CN 201910776951A CN 110534699 A CN110534699 A CN 110534699A
- Authority
- CN
- China
- Prior art keywords
- anode plate
- parts
- ionic cell
- graphene
- lithium ionic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 present invention relates to field of lithium ion battery, more specifically, the present invention relates to a kind of anode plate for lithium ionic cell, by weight, including following raw material: 70-75 parts of aerosil, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 parts of conductive agent, 0-1 parts of dispersing agent, 0.5-1 parts of thickener, 145-150 parts of water.The present invention is prepared for anode plate for lithium ionic cell using nitrogen-doped graphene and modified polyimide resin, nitrogen-doped graphene and modified polyimide resin have synergistic effect, the volume expansion of negative electrode material can be effectively inhibited during embedding de- lithium, stablize circulation, to improve the comprehensive performance of lithium ion battery.Simultaneously, the anode plate for lithium ionic cell large specific surface area that the present invention is prepared, specific capacitance is high, and it is flexible higher, and be coated using special process, after being coated on negative electrode tab surface cure, gained negative electrode tab surface is more smooth, harsh feeling is weak, therefore diaphragm can be effectively prevent to be pierced, and extends battery.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly it relates to a kind of anode plate for lithium ionic cell and its
Preparation method.
Background technique
In recent years, the high speed development of portable electronic device, electric tool and electric vehicle engineering is to lithium ion battery
Performance more stringent requirements are proposed, thus excite height ratio capacity of new generation, long circulation life lithium ion battery research.
Lithium ion battery is mainly made of electrolyte, diaphragm, positive and negative pole material, has high-energy-density density, high voltage, long-life, nothing
The characteristics such as memory effect, self discharge be small are portable cells most widely used at present.
Compared with the carbons negative electrode material of current commercialization, silicium cathode material has higher specific capacity and energy density, because
This is considered as potential next-generation lithium ion battery negative material.But in actual use, silicium cathode material is embedding de-
Lithium process can generate violent volume change, cause material dusting, coating from collection liquid surface peel off and solid electrolyte phase boundary
The rupture repeatedly and generation of facial mask, the cyclical stability of material is not high, and battery life is shorter.Solve the actual use of silicium cathode material
In the process the problem of volume expansion, generally use three kinds of methods: the first is improved to silicon materials itself, by reducing silicon
The partial size of material itself makes its nanosizing or by the way that silicon materials are compound with other materials；Second is to electrolyte and bonding
Agent is modified；The third is improved to electrode current collecting body and electrode structure.
Improving to silicon materials itself is the very effective method of solution silicium cathode material volume expansion, but after improving
Silicium cathode material cycle performance it is poor；Improving to electrolyte, binder, electrode current collecting body and electrode structure can make
The volume expansion problem of silicium cathode material is improved, but does not still solve the expansion issues of silicon inherently.Cause
This, the present invention specifically addresses above-mentioned silicium cathode materials can generate violent volume change in embedding de- lithium process, cause material powder
Change, coating are peeled off from collection liquid surface and SEI film ruptures repeatedly and are generated, so as to cause the circulation of material
Stability is not high, the short problem of battery life.
Summary of the invention
To solve the above-mentioned problems, first aspect of the present invention provides a kind of anode plate for lithium ionic cell, by weight
Meter, including following raw material: 70-75 parts of aerosil, 70-75 parts of graphene, 1-2.5 parts of binder, conductive agent 0.5-1
Part, 0-1 parts of dispersing agent, 0.5-1 parts of thickener, 145-150 parts of water.
As a kind of perferred technical scheme, the graphene is nitrogen-doped graphene.
As a kind of perferred technical scheme, the nitrogen-doped graphene the preparation method is as follows:
A) graphene is carried out to ultrasonic disperse in deionized water, to obtain uniform dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), and is uniformly mixed and obtains mixture；
C) mixture obtained by step b) is placed in the autoclave with teflon lined, it is anti-at 85-90 DEG C
2-3h is answered, is then heated to 210-250 DEG C, reacts 10-12h, nitrogen-doped graphene is finally made.
As a kind of perferred technical scheme, the mass ratio of the graphene and nitrogen dopant is 1:(0.2-0.8).
As a kind of perferred technical scheme, in step b), the nitrogen dopant is the mixing of triethanolamine and guanidine carbonate
Object.
As a kind of perferred technical scheme, the mass ratio of the triethanolamine and guanidine carbonate is 1:(0.5-2).
As a kind of perferred technical scheme, the binder is modified polyimide resin.
As a kind of perferred technical scheme, the modified polyimide resin the preparation method is as follows:
1) carboxylic diamine derivative is dissolved in n,N-dimethylacetamide solvent, aromatic dicarboxylic acid anhydride list is added
Body is reacted, and polyamic acid solution is obtained；
2) dehydrating agent and catalyst reaction 5-10h is added in gained polyamic acid solution in step 1), final be made changes
Property polyimide resin.
As a kind of perferred technical scheme, in step 1), the carboxylic diamine derivative is 3,4- diamino -2-
Naphthoic acid.
The second aspect of the present invention provides a kind of preparation method of anode plate for lithium ionic cell, and the preparation method is such as
Under:
I) aerosil, graphene are added in water, after mixing evenly successively add binder, conductive agent,
Dispersing agent, thickener are ground up, sieved after being uniformly dispersed, and negative electrode slurry is made；
Ii) by step I in coater oven) gained negative electrode slurry be applied to negative current collector surface, be then cold-pressed
It rolls, is then toasted under vacuum-pumping conditions, negative electrode tab is made.
The utility model has the advantages that the present invention is prepared for negative electrode of lithium ion battery using nitrogen-doped graphene and modified polyimide resin
Piece, nitrogen-doped graphene and modified polyimide resin have synergistic effect, can effectively inhibit cathode during embedding de- lithium
The volume expansion of material stablizes circulation, to improve the comprehensive performance of lithium ion battery.Meanwhile the lithium that the present invention is prepared
Ion battery negative electrode tab large specific surface area, specific capacitance is high, and flexible higher, and is coated using special process, applies
After being distributed in negative electrode tab surface cure, gained negative electrode tab surface is more smooth, and harsh feeling is weak, therefore diaphragm can be effectively prevent to be pierced
It wears, extends battery.
Specific embodiment
It is further clear, complete that the technical characteristic work in technical solution is provided to the present invention With reference to embodiment
Description, not to the limitation of its protection scope.
Word " preferred ", " preferred " in the present invention etc. refer to, can provide in some cases certain beneficial to effect
The embodiment of the present invention of fruit.However, other embodiments are also likely to be preferred under identical circumstances or in other situations
's.In addition, do not imply that other embodiments are unavailable to the expression of one or more preferred embodiments, be also not intended to by
Other embodiments exclude except the scope of the present invention.
First aspect of the present invention provides a kind of anode plate for lithium ionic cell, by weight, including following raw material: two
70-75 parts of silica aerogel, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 parts of conductive agent, 0-1 parts of dispersing agent increase
Thick dose 0.5-1 parts, 145-150 parts of water.
In a preferred embodiment, by weight, including following raw material: 73 parts of aerosil, stone
73 parts of black alkene, 2 parts of binder, 0.8 part of conductive agent, 0.5 part of dispersing agent, 0.6 part of thickener, 147 parts of water.
<aerosil>
Aerosil of the present invention is also referred to as " blue smoke ", " solid cigarette ", with nano-porous structure (2
~100nm), low-density, low-k (1.1~2.5), low thermal conductivity (0.013~0.025w/mk), high porosity
(65%~99%), high-specific surface area (300~1000m2/ g) the features such as, it is aobvious in aspects such as mechanics, acoustics, calorifics, optics
Peculiar property is shown, space flight and aviation, petrochemical industry, electric power, ship, new-energy automobile and lithium battery, heating power are widely used in
Pipeline, building keep warm or cold, the fields such as LNG cold chain.
The present invention is not particularly limited the aerosil, can be commonly used in the art various two
Silica aerogel can be prepared, such as the aerosil that can be prepared includes but is not limited to pass through colloidal sol-
Gel method is prepared；It can also be commercially available, such as the aerosil being available commercially includes but is not limited to
It buys from Jiangxi An Deli high and new technology Co., Ltd.
<graphene>
Graphene (Graphene) of the present invention be one kind by carbon atom with sp2It is in honeycomb that hybridized orbit, which forms hexangle type,
The two-dimentional carbon nanomaterial of lattice.
The present invention is not particularly limited the graphene, can be conventional use of various graphenes, can prepare
It obtains, such as the graphene that can be prepared includes but unlimited is by mechanically pulling off method, oxidation-reduction method, epitaxy method, carbon
SiClx epitaxy, He Mofa, chemical vapour deposition technique are prepared；It can also be commercially available, such as be available commercially
Graphene includes but is not limited to buy from Nanjing Xian Feng Nono-material Science & Technology Ltd..
In one embodiment, the graphene is nitrogen-doped graphene, the preparation method is as follows:
A) graphene is carried out to ultrasonic disperse in deionized water, to obtain uniform dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), and is uniformly mixed and obtains mixture；
C) mixture obtained by step b) is placed in the autoclave with teflon lined, it is anti-at 85-90 DEG C
2-3h is answered, is then heated to 210-250 DEG C, reacts 10-12h, nitrogen-doped graphene is finally made.
In a preferred embodiment, the nitrogen-doped graphene the preparation method is as follows:
A) graphene (model XF001W) is subjected to ultrasonic disperse in deionized water, to obtain uniform dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), and is uniformly mixed and obtains mixture；
C) mixture obtained by step b) is placed in the autoclave with teflon lined, is reacted at 90 DEG C
2h is then heated to 220 DEG C, reacts 10h, and nitrogen-doped graphene is finally made.
In one embodiment, the mass ratio of the graphene and nitrogen dopant is 1:(0.2-0.8).
In a preferred embodiment, the mass ratio of the graphene and nitrogen dopant is 1:0.5.
In one embodiment, the graphene and the mass ratio of deionized water are 1:1.
(nitrogen dopant)
Nitrogen dopant of the present invention is the additive rich in nitrogen source, can introduce nitrogen atom structure in the material.
Nitrogen dopant of the present invention be selected from urea, melamine, ammonium hydroxide, triethanolamine, hydrazine hydrate, guanethidine, pyrroles,
The combination of one or more of aniline, guanidine carbonate, phosphoguanidine, guanidine hydrochloride, urea phosphate.
In one embodiment, the nitrogen dopant be triethanolamine (CAS:102-71-6) and guanidine carbonate (CAS:
Mixture 593-85-1).
In a preferred embodiment, the mass ratio of the triethanolamine and guanidine carbonate is 1:(0.5-2).
In a kind of preferred embodiment, the mass ratio of the triethanolamine and guanidine carbonate is 1:1.
The application introduces nitrogen heteroatom by the way that nitrogen dopant is added in graphene, improves the specific capacitance of negative electrode material
Amount.Since the specific capacitance of negative electrode material is smaller, by introducing nitrogen heteroatom in negative electrode material, the ratio of negative electrode material is improved
Capacitance.
The applicant has been surprisingly found that, when being modified with two kinds of nitrogen dopants of triethanolamine and guanidine carbonate to graphene,
Further improve lithium ion battery cyclical stability, applicant speculate the possible reason is: on the one hand in hydro-thermal reaction plus
After entering triethanolamine and guanidine carbonate, thermal decomposition can be made to react collective effect with group, the nitrogen of introducing is finally with pyridine nitrogen, pyrrole
Nitrogen, quaternary nitrogen and four kinds of graphite nitrogen different forms are coughed up to exist；Another aspect triethanolamine and guanidine carbonate interaction, make graphene
Surface produces more defect sites, to generate more uniform curlings and fold on the surface of graphene.Therefore, it introduces
Bond strength of the nitrogen in negative electrode material it is more preferable, can promote insertion of lithium ion during embedding de- lithium (i.e. charge and discharge) and
It is detached from.
<binder>
The guarantee of binder of the present invention adhesion strength between abrasive material and matrix.
Binder of the present invention is selected from butadiene-styrene rubber, styrene butadiene ribber, carboxymethyl cellulose, gathers inclined difluoro second
The combination of one or more of alkene, polyimides, acrylic resin, butyral resin.
In one embodiment, the binder is modified polyimide resin, the preparation method is as follows:
1) carboxylic diamine derivative is dissolved in n,N-dimethylacetamide solvent, aromatic dicarboxylic acid anhydride list is added
Body is reacted, and polyamic acid solution is obtained；
2) dehydrating agent and catalyst reaction 5-10h is added in gained polyamic acid solution in step 1), final be made changes
Property polyimide resin.
In a preferred embodiment, the modified polyimide resin the preparation method is as follows:
1) carboxylic diamine derivative is dissolved in n,N-dimethylacetamide solvent, pyromellitic acid anhydride is added
It is reacted, obtains polyamic acid solution；
2) dehydrating agent acetic anhydride is added in gained polyamic acid solution in step 1) and catalyst of triethylamine reacts 7h, most
Obtained modified polyimide resin eventually.
In a kind of preferred embodiment, carboxylic diamine derivative, n,N-dimethylacetamide, equal benzene tetramethyl
Acid dianhydride, acetic anhydride, triethylamine molar ratio be 1:5:1:2:2.
(carboxylic diamine derivative)
In one embodiment, the example of the carboxylic diamine derivative, including but not limited to: 4,6- diaminos
Base -1,3- phthalic acid (CAS:13324-94-2), 2,5- diamino -4- methyl benzoic acid (CAS:13066-80-3), 2,3-
Diaminobenzoic acid (CAS:603-81-6), 2,4- diaminobenzoic acid (CAS:611-03-0), 2,5- diaminobenzoic acid
(CAS:610-74-2), 2,6- diaminobenzoic acid (CAS:102000-59-9), 3,4- diaminobenzoic acid (CAS:619-05-
6), 3,5- diaminobenzoic acid (CAS:535-87-5), 3,4- diamino -2- naphthoic acid (CAS:612806-13-0), 2,6- bis-
Amino -1- naphthoic acid (CAS:46390-04-9), 3,4- diaminostilbene-naphthoic acid (CAS:675877-59-5).
In a preferred embodiment, the carboxylic diamine derivative is 3,4- diamino -2- naphthoic acid
(CAS:612806-13-0)。
The application strengthens the connection between negative electrode material and collector by the way that polyimides is added.Due to the phase of polyimides
Capacitive is poor, is modified by using carboxylic diamine derivative to polyimides, improves the compatibility of polyimides,
Strengthen the connection between negative electrode material and collector.
The applicant has been surprisingly found that, when the carboxylic diamine derivative is 3,4- diamino -2- naphthoic acid, into one
Step improves lithium ion battery cyclical stability, applicant speculate the possible reason is: one side modified polyimide resin can
Composite conducting elasticity inhibition layer is formed by active force with graphene, aerosil；Another aspect modified polyimide
Active group on resin alleviates the irregular stress to SEI film of each point volume caused by negative terminal surface lithium deposition,
To improve lithium ion battery cyclical stability.
In one embodiment, the mass ratio of the binder and graphene is 1:(30-70).
In a preferred embodiment, the mass ratio of the binder and graphene is 1:(32-45).
In a kind of preferred embodiment, the mass ratio of the binder and graphene is 1:36.5.
Applicant has been surprisingly found that, when the mass ratio of binder and graphene is 1:(30-70) when, the circulation of lithium ion battery
Stability is preferable, this may be since modified polyimide resin and nitrogen-doped graphene, the thickener etc. in system can be sent out
Good synergistic effect is waved, one side modified polyimide resin can interact with nitrogen-doped graphene and generate composite conducting bullet
Property inhibition layer, inhibits the volume expansion of negative electrode material；Pyridine nitrogen, pyrroles's nitrogen, quaternary nitrogen and stone in another aspect nitrogen-doped graphene
Four kinds of black nitrogen different nitrogen can realize the uniform of negative terminal surface lithium metal simultaneously with different component in system and Interaction of substituents
Deposition, to improve lithium ion battery cyclical stability.When the mass ratio of binder and graphene is 1:36.5, lithium ion
The cyclical stability of battery is best.When the mass ratio of binder and graphene is less than 1:70, modified polyimide resin and body
Nitrogen-doped graphene, thickener in system etc. can not play good synergistic effect, and the volume expansion of negative electrode material is violent, lithium
Ion battery cyclical stability is poor；When the mass ratio of binder and graphene be greater than 1:30 when, modified polyimide resin with
Nitrogen-doped graphene, thickener in system etc. can not play good synergistic effect, and negative terminal surface lithium metal deposition is irregular
Uneven, lithium ion battery cyclical stability is poor.
<conductive agent>
Conductive agent of the present invention is usually to add to guarantee that electrode has good charge-discharge performance in pole piece production
Enter a certain amount of conductive materials, plays the role of collecting micro-current between active material, between active material and collector, with
The contact resistance for reducing electrode accelerates the rate travel of electronics, while can also effectively improve lithium ion moving in electrode material
Rate is moved, to improve the efficiency for charge-discharge of electrode.
In one embodiment, the conductive agent is selected from artificial graphite, natural graphite, graphene, Ketjen black, carbon nanometer
The combination of one or more of pipe, carbon fiber, acetylene black, carbon black, conducting polymer.
In a preferred embodiment, the conductive agent is carbon nanotube, acetylene black.
In a kind of preferred embodiment, the conductive agent is acetylene black (CAS:1333-86-4), is purchased from Shanghai promise
Safe Chemical Co., Ltd..
<dispersing agent>
Dispersing agent (Dispersant) of the present invention is one kind in the molecule while having lipophilicity and two kinds of hydrophily
The interfacial agent of opposite nature.
In one embodiment, it is (next to be selected from carboxymethyl cellulose, hydroxyethyl cellulose, KELCOGEL for the dispersing agent
From CPKelco company), GELMATE (Lai Zi great SUMITOMO CHEMICAL pharmaceutical Co. Ltd), pectin, alginic acid, guar gum, locust tree
It is bean gum, gum arabic, dextrin, aldose, D-sorbite, lactose, rice starch, the polysaccharide of sucrose and monosaccharide, sodium taurocholate, bright
The combination of one or more of glue, polyvinyl alcohol, neopelex, NDZ201, KH550, KH570.
In a preferred embodiment, the dispersing agent is carboxymethyl cellulose, gelatin and water-soluble polysaccharide.
In a kind of preferred embodiment, the dispersing agent is carboxymethyl cellulose (CAS:9000-11-7), is purchased from
Changzhou Luo Wan Biotechnology Co., Ltd.
<thickener>
Thickener of the present invention is a kind of auxiliary rheological agents, can not only coating be made to thicken, and prevents sagging occur in construction
Phenomenon, and the excellent mechanical performance of coating and storage stability can be assigned.For water paint lower for viscosity, right and wrong
An often important analog assistant.
In one embodiment, the thickener is selected from inorganic thickening agent, cellulose ether, natural polymer, synthesis height
The combination of one or more of molecule, solvay-type organo-metallic compound.
As the example of inorganic thickening agent, including but not limited to: fume colloidal silica, sodium bentonite, organobentonite,
Diatomite, attapulgite soil, molecular sieve, Silica hydrogel.
As the example of cellulose ether, including but not limited to: methylcellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyl
Propyl methocel, carboxymethyl cellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose.
As the example of natural polymer, including but not limited to: starch, gelatin, sodium alginate, casein, guar gum, first
Shell amine, gum arabic, xanthan gum, soybean protein glue, natural rubber, lanolin, agar.
As high molecular example is synthesized, including but not limited to: polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone,
Polyethylene glycol oxide, modified paraffin resin, carbomer, polyacrylic acid, Sodium Polyacrylate, Polyacrylate Emulsion, suitable fourth
Rubber, butadiene-styrene rubber, polyurethane, modified polyurea, low-molecular polyethylene wax, polycarboxylic acids, polyethylene oxide.
As the example of solvay-type organo-metallic compound, including but not limited to: amino alcohol solvay-type phthalate ester.
In a preferred embodiment, the thickener is gelatin (CAS:9000-70-8), is purchased from Shandong Feng Taisheng
Object Science and Technology Ltd..
The second aspect of the invention provides a kind of preparation method of anode plate for lithium ionic cell, and the preparation method is such as
Under:
I) aerosil, graphene are added in water, after mixing evenly successively add binder, conductive agent,
Dispersing agent, thickener are ground up, sieved after being uniformly dispersed, and negative electrode slurry is made；
Ii) by step I in coater oven) gained negative electrode slurry be applied to negative current collector surface, be then cold-pressed
It rolls, is then toasted under vacuum-pumping conditions, negative electrode tab is made.
Embodiment
Embodiment 1
Embodiment 1 provides a kind of anode plate for lithium ionic cell, by weight, including following raw material: silica gas
73 parts of gel, 73 parts of graphene, 2 parts of binder, 0.8 part of conductive agent, 0.5 part of dispersing agent, 0.6 part of thickener, 147 parts of water；
The aerosil is purchased from Jiangxi An Deli high and new technology Co., Ltd；
The graphene is nitrogen-doped graphene, the preparation method is as follows:
A) graphene is carried out to ultrasonic disperse in deionized water, to obtain uniform dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), and is uniformly mixed and obtains mixture；
C) mixture obtained by step b) is placed in the autoclave with teflon lined, is reacted at 90 DEG C
2h is then heated to 220 DEG C, reacts 10h, and nitrogen-doped graphene is finally made；
The mass ratio of the graphene and nitrogen dopant is 1:0.5；
The graphene and the mass ratio of deionized water are 1:1；
Graphene described in step a) is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., model XF001W；
Nitrogen dopant described in step b) is the mixture of triethanolamine and guanidine carbonate, the triethanolamine and guanidine carbonate
Mass ratio is 1:1；
The binder is modified polyimide resin, the preparation method is as follows:
1) carboxylic diamine derivative is dissolved in n,N-dimethylacetamide solvent, pyromellitic acid anhydride is added
It is reacted, obtains polyamic acid solution；
2) dehydrating agent acetic anhydride is added in gained polyamic acid solution in step 1) and catalyst of triethylamine reacts 7h, most
Obtained modified polyimide resin eventually；
The carboxylic diamine derivative, DMAC N,N' dimethyl acetamide, pyromellitic acid anhydride, acetic anhydride, triethylamine
Molar ratio be 1:5:1:2:2；
Carboxylic diamine derivative described in step 1) is 3,4- diamino -2- naphthoic acid (CAS:612806-13-0)；
The conductive agent is acetylene black (CAS:1333-86-4), is purchased from Shanghai Nuo Tai Chemical Co., Ltd.；
The dispersing agent is carboxymethyl cellulose (CAS:9000-11-7), is purchased from Changzhou Luo Wan Biotechnology Co., Ltd；
The thickener is gelatin (CAS:9000-70-8), is purchased from Shandong Feng Tai Biotechnology Co., Ltd；
The anode plate for lithium ionic cell the preparation method is as follows:
I) aerosil, graphene are added in water, after mixing evenly successively add binder, conductive agent,
Dispersing agent, thickener are ground up, sieved after being uniformly dispersed, and negative electrode slurry is made；
Ii) by step I in coater oven) gained negative electrode slurry be applied to negative current collector surface, be then cold-pressed
It rolls, is then toasted under vacuum-pumping conditions, negative electrode tab is made.
Embodiment 2
Embodiment 2 provides a kind of anode plate for lithium ionic cell, by weight, including following raw material: silica gas
75 parts of gel, 75 parts of graphene, 2.5 parts of binder, 1 part of conductive agent, 1 part of dispersing agent, 1 part of thickener, 150 parts of water；
The aerosil is purchased from Jiangxi An Deli high and new technology Co., Ltd；
The graphene is nitrogen-doped graphene, the preparation method is as follows:
A) graphene is carried out to ultrasonic disperse in deionized water, to obtain uniform dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), and is uniformly mixed and obtains mixture；
C) mixture obtained by step b) is placed in the autoclave with teflon lined, is reacted at 90 DEG C
2h is then heated to 220 DEG C, reacts 10h, and nitrogen-doped graphene is finally made；
The mass ratio of the graphene and nitrogen dopant is 1:0.8；
The graphene and the mass ratio of deionized water are 1:1；
Graphene described in step a) is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., model XF001W；
Nitrogen dopant described in step b) is the mixture of triethanolamine and guanidine carbonate, the triethanolamine and guanidine carbonate
Mass ratio is 1:2；
The binder is modified polyimide resin, and the preparation method is the same as that of Example 1；
The conductive agent is acetylene black (CAS:1333-86-4), is purchased from Shanghai Nuo Tai Chemical Co., Ltd.；
The dispersing agent is carboxymethyl cellulose (CAS:9000-11-7), is purchased from Changzhou Luo Wan Biotechnology Co., Ltd；
The thickener is gelatin (CAS:9000-70-8), is purchased from Shandong Feng Tai Biotechnology Co., Ltd；
The preparation method is the same as that of Example 1 for the anode plate for lithium ionic cell.
Embodiment 3
Embodiment 3 provides a kind of anode plate for lithium ionic cell, by weight, including following raw material: silica gas
70 parts of gel, 70 parts of graphene, 1 part of binder, 0.5 part of conductive agent, 0 part of dispersing agent, 0.5 part of thickener, 145 parts of water；
The aerosil is purchased from Jiangxi An Deli high and new technology Co., Ltd；
The graphene is nitrogen-doped graphene, the preparation method is as follows:
A) graphene is carried out to ultrasonic disperse in deionized water, to obtain uniform dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), and is uniformly mixed and obtains mixture；
C) mixture obtained by step b) is placed in the autoclave with teflon lined, is reacted at 90 DEG C
2h is then heated to 220 DEG C, reacts 10h, and nitrogen-doped graphene is finally made；
The mass ratio of the graphene and nitrogen dopant is 1:0.2；
The graphene and the mass ratio of deionized water are 1:1；
Graphene described in step a) is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., model XF001W；
Nitrogen dopant described in step b) is the mixture of triethanolamine and guanidine carbonate, the triethanolamine and guanidine carbonate
Mass ratio is 1:0.5；
The binder is modified polyimide resin, and the preparation method is the same as that of Example 1；
The conductive agent is acetylene black (CAS:1333-86-4), is purchased from Shanghai Nuo Tai Chemical Co., Ltd.；
The dispersing agent is carboxymethyl cellulose (CAS:9000-11-7), is purchased from Changzhou Luo Wan Biotechnology Co., Ltd；
The thickener is gelatin (CAS:9000-70-8), is purchased from Shandong Feng Tai Biotechnology Co., Ltd；
The preparation method is the same as that of Example 1 for the anode plate for lithium ionic cell.
Embodiment 4
Embodiment 4 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, by the mass ratio of the graphene and nitrogen dopant replace
For 1:0.05.
Embodiment 5
Embodiment 5 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, by the mass ratio of the graphene and nitrogen dopant replace
For 1:1.5.
Embodiment 6
Embodiment 6 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the nitrogen-doped graphene is replaced with into XF001W.
Embodiment 7
Embodiment 7 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the nitrogen dopant is replaced with into hydrazine hydrate.
Embodiment 8
Embodiment 8 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the nitrogen dopant is replaced with into triethanolamine.
Embodiment 9
Embodiment 9 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the nitrogen dopant is replaced with into guanidine carbonate.
Embodiment 10
Embodiment 10 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the nitrogen dopant is replaced with into triethanolamine and trimerization
Cyanamide.
Embodiment 11
Embodiment 11 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the nitrogen dopant is replaced with into guanidine carbonate and urea.
Embodiment 12
Embodiment 12 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, by the mass ratio of the triethanolamine and guanidine carbonate replace
For 1:0.2.
Embodiment 13
Embodiment 13 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, by the mass ratio of the triethanolamine and guanidine carbonate replace
For 1:5.
Embodiment 14
Embodiment 14 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the content of the binder is replaced with 3.5 parts.
Embodiment 15
Embodiment 15 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, by the binder replace with butadiene-styrene rubber (CAS:
9003-55-8), it is purchased from the good marble Co., Ltd of Yueyang Ba Ling.
Embodiment 16
Embodiment 16 provides a kind of anode plate for lithium ionic cell, additionally provides a kind of preparation of anode plate for lithium ionic cell
Method, specific embodiment with embodiment 1, the difference is that, the carboxylic diamine derivative is replaced with 3,4-
Diaminobenzoic acid.
Performance Evaluation:
The preparation of based lithium-ion battery positive plate: by the positive electrode active materials LiCoO of 94 parts by weight2, 2 parts by weight conductive agent
The conductive carbon SP and binder PVDF of 4 parts by weight is uniformly mixed in solvent DMAC N,N' dimethyl acetamide and anode sizing agent is made；It will
Anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil, is cold-pressed after dry to bulk density 4g/cc, sliced obtained lithium ion
Battery anode slice.
The preparation of lithium-ion battery electrolytes: by the ethylene carbonate (EC) of 50 parts by weight, the methyl ethyl carbonate of 45 parts by weight
Ester (DEC) and the fluorinated ethylene carbonate (FEC) of 5 parts by weight are sufficiently mixed uniformly, with lithium hexafluoro phosphate (LiPF6) it is solute,
Lithium-ion battery electrolytes, LiPF is made6Concentration be 1mol/L.
The preparation of lithium ion battery: by 1~16 gained anode plate for lithium ionic cell of embodiment and based lithium-ion battery positive plate,
Polyethylene (PE) isolation film is rolled, the lithium-ion electric for being 80mm with a thickness of 4mm, width 35mm, length is made in packaging technology
Core；The vacuum bakeout 14h at 80 DEG C injects lithium-ion battery electrolytes and stands 25h；The constant current of 0.1C is used at 35 DEG C
4.5V is charged to, 0.05C is then dropped to 4.5V constant voltage charging to electric current, then be discharged to the constant current of 0.5C
3.0V is repeated charge and discharge 2 times, lithium ion battery is finally charged to 3.5V with the constant current of 0.5C and completes partial volume, lithium is made
Ion battery.
1, negative electrode tab expansion rate after partial volume
Negative electrode tab expansion rate is calculated as follows after partial volume:
Negative electrode tab expansion rate (%) after partial volume=[(negative electrode tab thickness-negative pole currect collecting body thickness after partial volume)/it is (negative after cold pressing
Pole thickness-negative pole currect collecting body thickness) -1] × 100%, wherein negative electrode tab thickness is measured with screw micrometer.
2, battery capacity conservation rate is tested: charging/discharging voltage range is set as 0~3V, is followed under 0.5C current density
Ring test, and record the discharge capacity recycled every time.
The capacity retention ratio of lithium ion battery is calculated as follows:
N times circulation volume conservation rate (%)=[n-th cyclic discharge capacity/for the first time discharge capacity] × 100%.
3, cell expansion rate after recycling
Cell expansion rate calculates as follows after circulation:
Cell expansion rate (%) after circulation=[battery is thick after (cell thickness after cell thickness-partial volume after circulation)/partial volume
Degree] × 100%, wherein cell thickness is tested with high metric, cell expansion rate level representation form the positive/negative plate of battery
Expansion rate is horizontal.
Table 1 gives the performance of lithium ion battery test result of 1~16 gained anode plate for lithium ionic cell of embodiment.
The performance of lithium ion battery test result of 1 embodiment of table, 1~16 gained anode plate for lithium ionic cell
By 1 performance of lithium ion battery test result of table it is found that anode plate for lithium ionic cell provided by the invention overcome it is negative
Volume expansion of pole material during embedding de- lithium, cathode expansion rate is small, good cycle, excellent combination property.
Example above-mentioned is merely illustrative, and is used to explain the present invention some features of the method.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (10)
1. a kind of anode plate for lithium ionic cell, which is characterized in that by weight, including following raw material: aerosil
70-75 parts, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 parts of conductive agent, 0-1 parts of dispersing agent, 0.5-1 parts of thickener,
145-150 parts of water.
2. anode plate for lithium ionic cell according to claim 1, which is characterized in that the graphene is N doping graphite
Alkene.
3. anode plate for lithium ionic cell according to claim 2, which is characterized in that the preparation side of the nitrogen-doped graphene
Method is as follows:
A) graphene is carried out in water to ultrasound, obtain dispersion liquid；
B) nitrogen dopant is added into dispersion liquid obtained by step a), obtains mixture；
C) mixture obtained by step b) is placed in autoclave, reacts 2-3h at 85-90 DEG C, is then heated to 210-250
DEG C, 10-12h is reacted, nitrogen-doped graphene is finally made.
4. anode plate for lithium ionic cell according to claim 3, which is characterized in that the matter of the graphene and nitrogen dopant
Amount is than being 1:(0.2-0.8).
5. anode plate for lithium ionic cell according to claim 3, which is characterized in that in step b), the nitrogen dopant is
The mixture of triethanolamine and guanidine carbonate.
6. anode plate for lithium ionic cell according to claim 5, which is characterized in that the matter of the triethanolamine and guanidine carbonate
Amount is than being 1:(0.5-2).
7. anode plate for lithium ionic cell according to claim 1, which is characterized in that the binder is modified polyimide
Resin.
8. anode plate for lithium ionic cell according to claim 7, which is characterized in that the system of the modified polyimide resin
Preparation Method is as follows:
1) carboxylic diamine derivative is dissolved in n,N-dimethylacetamide solvent, be added aromatic dicarboxylic anhydride monomer into
Row reaction, obtains polyamic acid solution；
2) dehydrating agent and catalyst reaction 5-10h is added in gained polyamic acid solution in step 1), it is final to be made modified poly-
Imide resin.
9. anode plate for lithium ionic cell according to claim 8, which is characterized in that in step 1), described carboxylic two
Amine derivative is 3,4- diamino -2- naphthoic acid.
10. a kind of preparation method of basis such as described in any item anode plate for lithium ionic cell of claim 1-9, feature exist
In, it is described the preparation method is as follows:
I) aerosil, graphene are added in water, then add binder, conductive agent, dispersing agent, thickener, so
After be ground up, sieved, be made negative electrode slurry；
Ii) by step I in coater oven) gained negative electrode slurry be applied to negative current collector surface, then carry out cold pressing roll,
Then it is toasted under vacuum-pumping conditions, negative electrode tab is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910776951.0A CN110534699B (en) | 2019-08-22 | 2019-08-22 | Preparation method of lithium ion battery negative plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910776951.0A CN110534699B (en) | 2019-08-22 | 2019-08-22 | Preparation method of lithium ion battery negative plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110534699A true CN110534699A (en) | 2019-12-03 |
| CN110534699B CN110534699B (en) | 2021-07-13 |
Family
ID=68662464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910776951.0A Active CN110534699B (en) | 2019-08-22 | 2019-08-22 | Preparation method of lithium ion battery negative plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110534699B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112520719A (en) * | 2020-11-16 | 2021-03-19 | 阜阳申邦新材料技术有限公司 | Polyimide modified carbon-silicon negative electrode material and preparation method thereof |
| CN112599776A (en) * | 2020-12-14 | 2021-04-02 | 杭州肄康新材料有限公司 | Preparation method of calamine cream gel applied to alkaline zinc-manganese battery |
| CN112863901A (en) * | 2021-03-03 | 2021-05-28 | 郑州航空工业管理学院 | Preparation method of supercapacitor slurry |
| CN113178570A (en) * | 2021-03-10 | 2021-07-27 | 深圳市盛邦科技有限公司 | LiMn with long cycle life2O4Lithium battery material |
| CN114258603A (en) * | 2021-03-31 | 2022-03-29 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736584A (en) * | 2005-08-03 | 2006-02-22 | 北京科技大学 | Method for preparing nitrogen doped nano titanium dioxide photocatalyst with visible light activity by direct heat treatment method |
| KR20140056570A (en) * | 2012-10-29 | 2014-05-12 | 한국과학기술연구원 | Method for doped graphene using microwave |
| CN107431207A (en) * | 2015-02-05 | 2017-12-01 | 株式会社 Pi 技术研究所 | Electrode binding agent resin, electrode of lithium secondary cell and the lithium secondary battery of lithium secondary battery |
| CN108199006A (en) * | 2017-12-28 | 2018-06-22 | 长沙善道新材料科技有限公司 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene-silica negative plate of low roughness |
| CN109950493A (en) * | 2019-03-27 | 2019-06-28 | 东莞东阳光科研发有限公司 | Silica aerogel/micro- swollen graphite composite material, preparation method and application |
-
2019
- 2019-08-22 CN CN201910776951.0A patent/CN110534699B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736584A (en) * | 2005-08-03 | 2006-02-22 | 北京科技大学 | Method for preparing nitrogen doped nano titanium dioxide photocatalyst with visible light activity by direct heat treatment method |
| KR20140056570A (en) * | 2012-10-29 | 2014-05-12 | 한국과학기술연구원 | Method for doped graphene using microwave |
| CN107431207A (en) * | 2015-02-05 | 2017-12-01 | 株式会社 Pi 技术研究所 | Electrode binding agent resin, electrode of lithium secondary cell and the lithium secondary battery of lithium secondary battery |
| CN108199006A (en) * | 2017-12-28 | 2018-06-22 | 长沙善道新材料科技有限公司 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene-silica negative plate of low roughness |
| CN109950493A (en) * | 2019-03-27 | 2019-06-28 | 东莞东阳光科研发有限公司 | Silica aerogel/micro- swollen graphite composite material, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 刘兆恩: ""杂原子掺杂石墨烯气凝胶的制备及其在超级电容器中的应用"", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》 * |
| 刘雄锋: ""二氧化硅气凝胶的制备及其在锂离子电池中电化学性能研究"", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技Ⅱ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112520719A (en) * | 2020-11-16 | 2021-03-19 | 阜阳申邦新材料技术有限公司 | Polyimide modified carbon-silicon negative electrode material and preparation method thereof |
| CN112520719B (en) * | 2020-11-16 | 2022-10-18 | 湖北斯诺新材料科技有限公司 | Polyimide modified carbon-silicon negative electrode material and preparation method thereof |
| CN112599776A (en) * | 2020-12-14 | 2021-04-02 | 杭州肄康新材料有限公司 | Preparation method of calamine cream gel applied to alkaline zinc-manganese battery |
| CN112863901A (en) * | 2021-03-03 | 2021-05-28 | 郑州航空工业管理学院 | Preparation method of supercapacitor slurry |
| CN113178570A (en) * | 2021-03-10 | 2021-07-27 | 深圳市盛邦科技有限公司 | LiMn with long cycle life2O4Lithium battery material |
| CN114258603A (en) * | 2021-03-31 | 2022-03-29 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| WO2022205109A1 (en) * | 2021-03-31 | 2022-10-06 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110534699B (en) | 2021-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110534699A (en) | A kind of preparation method of anode plate for lithium ionic cell | |
| CN108511685B (en) | Lithium ion battery negative plate containing conductive coating and preparation method thereof | |
| CN108511689B (en) | Lithium ion battery positive plate containing conductive coating and preparation method thereof | |
| CN110071292B (en) | Preparation method of lithium ion battery positive pole piece and positive pole piece | |
| CN103268942B (en) | The coating modified collector of a kind of nano-graphite | |
| CN108598414B (en) | Amorphous zinc oxide/carbon composite lithium ion battery cathode material and preparation method thereof | |
| CN103311514B (en) | A kind of preparation method of modification lithium-ion battery graphite cathode material | |
| CN103208618B (en) | Carbon in lithium ion battery sulphur composite positive pole and preparation method thereof | |
| CN105226254B (en) | A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application | |
| CN107634207A (en) | A kind of silicon mosaic redox graphene/graphite phase carbon nitride composite and its preparation and application | |
| CN113659125B (en) | Silicon-carbon composite material and preparation method thereof | |
| CN106654367B (en) | Method for preparing electrolyte membrane and solid lithium battery | |
| CN104617256B (en) | Nano zine oxide graphite graphene composite material and its preparation method and application | |
| CN108448080A (en) | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof | |
| CN112234182B (en) | High-capacity silicon-carbon material for lithium battery cathode and preparation method thereof | |
| CN106992318A (en) | A kind of lithium-ion-power cell and preparation method thereof | |
| CN107611411A (en) | A kind of preparation method and application of the classifying porous nitrogen-doped carbon bag silicon composite of three-dimensional | |
| CN107394138B (en) | Lithium ion battery cathode material structure, lithium ion battery and preparation method thereof | |
| CN106356556B (en) | A kind of lithium-ion-power cell with long service life and preparation method thereof | |
| CN104868159A (en) | Preparation method for modified graphite anode material | |
| CN112038637B (en) | Composite conductive agent, preparation method thereof and lithium ion battery | |
| CN112331839B (en) | MXene-doped and surface-coated modified lithium ion battery positive electrode material and preparation method thereof | |
| CN103078088B (en) | Lithium ion battery cathode material | |
| CN108520959B (en) | Water-based polymer-isocyanate-based electrode composite material and preparation method thereof | |
| CN107681159B (en) | Metal foil current collector for battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210618 Address after: No.19, Qinhuai North Road, Lishui Economic Development Zone, Nanjing, Jiangsu, 211299 Applicant after: Jiangsu Da Mao Niu New Material Co.,Ltd. Address before: No.157-1, Hongshan Road, Xuanwu District, Nanjing City, Jiangsu Province, 210000 Applicant before: Li Jindi |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |