CN107104227A - Anode material for lithium-ion batteries and preparation method thereof - Google Patents
Anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN107104227A CN107104227A CN201710391348.1A CN201710391348A CN107104227A CN 107104227 A CN107104227 A CN 107104227A CN 201710391348 A CN201710391348 A CN 201710391348A CN 107104227 A CN107104227 A CN 107104227A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H—ELECTRICITY
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- 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
- H01M2004/028—Positive electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to energy storage research field, more particularly to a kind of anode material for lithium-ion batteries, including nuclear structure and shell structure, the nuclear structure is second particle structure, and including the leading electric network with loose structure and the nanometer primary particle being filled in the porous leading electric network pore structure；The nanometer primary particle includes at least one of class lithium cobaltate by nm, nanometer lithium manganate, nano-grade lithium iron phosphate, nanometer nickel-cobalt manganese, nanometer nickel-cobalt aluminium, nanometer lithium nickelate, nanometer lithium-barium oxide, nanometer lithium-rich anode material；There is stronger chemical bond between the leading network structure and power is acted on；The nanometer primary particle is closely locked in the pore structure of the leading electric network by the chemical bond.So that it is guaranteed that the anode material for lithium-ion batteries has excellent chemical property.
Description
Technical field
The invention belongs to energy storage material technical field, more particularly to a kind of anode material for lithium-ion batteries and its preparation side
Method.
Background technology
Lithium ion battery is with its fast charging and discharging, low temperature performance well, specific energy is big, self-discharge rate is small, small volume, lightweight
Etc. advantage, since its birth, revolutionary change just is brought to energy storage field, is widely used in various portable electronics
In equipment and electric automobile.However as the improvement of people's living standards, higher Consumer's Experience is proposed to lithium ion battery
Higher requirement：Longer stand-by time, more quick charge/discharge rates etc.；Had to look for solve the above problems new
The more excellent electrode material of performance.
Current commercialized anode material for lithium-ion batteries, be semiconductor or insulator substantially, and material granule is in itself
Electric conductivity is excessively poor, in order to solve the above problems, and prior art mainly has obtains two by pelletizing after material granule nanosizing
Conductive material with excellent conductive capability etc. is added in secondary grain structure, primary particle balling process, to improve positive pole material
Expect the electric conductivity of integral particle；Coating technology is used simultaneously, material surface is coated, so as to increase leading for material surface
Electrical property.
But the primary particle of nanostructured is easily reunited, disperse difficulty big；And conventional conductive agent material, general size
Smaller (nanoscale), and specific surface area is larger, scattered difficulty is bigger.But when, to maximize conductive agent conductive effect and
The more excellent lithium ion cell positive second particle material of processability, it is necessary to ensure that nanometer primary particle and conductive agent are uniform
It is scattered.Meanwhile, contact area between the primary particle and conductive agent of nanostructured is smaller, gap is larger, therefore contact resistance
Relatively large, the positive electrode finished product internal resistance prepared is larger, so as to influence the lithium-ion electric using it as positive electrode
The chemical property in pond plays and (is mainly shown as that impedance is big, polarization is big, heating is serious).
In view of this, it is necessory to propose a kind of anode material for lithium-ion batteries and preparation method thereof, it can be by two kinds
The larger material (nanometer primary particle, conductive agent) of scattered difficulty is dispersed, while ensuring to be close-coupled between the two
Together, so as to prepare the anode material for lithium-ion batteries of function admirable.
The content of the invention
It is an object of the invention to：In view of the shortcomings of the prior art, a kind of anode material for lithium-ion batteries provided, bag
Nuclear structure and shell structure are included, the nuclear structure is second particle structure, and including the leading electric network with loose structure
And it is filled in the nanometer primary particle in the porous leading electric network pore structure；The nanometer primary particle includes nanometer cobalt
Sour lithium, nanometer lithium manganate, nano-grade lithium iron phosphate, nanometer nickel-cobalt manganese, nanometer nickel-cobalt aluminium, nanometer lithium nickelate, nanometer lithium-barium oxide,
At least one of nanometer lithium-rich anode material；There is stronger chemical bond between the leading network structure and power is acted on；Institute
Chemical bond is stated closely to be locked in the nanometer primary particle in the pore structure of the leading electric network.So that it is guaranteed that the lithium from
Sub- cell positive material has excellent chemical property.The present invention suitable for energy storage research field, institute it is in need once
Grain pelletizing obtains the material of second particle structure, specifically includes lithium ion anode material, ion cathode material lithium (such as graphite, silicon
Carbon, LiFePO4, alloy anode etc.) and other battery capacitor material (such as lithium-air battery, fuel cell, sodium ions
Battery, Zinc ion battery etc.).
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of anode material for lithium-ion batteries, including nuclear structure and shell structure, the nuclear structure are second particle structure, and
Including the leading electric network with loose structure and the nanometer one being filled in the porous leading electric network pore structure
Secondary particle；The nanometer primary particle includes class lithium cobaltate by nm, nanometer lithium manganate, nano-grade lithium iron phosphate, nanometer nickel-cobalt manganese, nanometer
At least one of nickel cobalt aluminium, nanometer lithium nickelate, nanometer lithium-barium oxide, nanometer lithium-rich anode material；The leading network knot
There is stronger chemical bond between structure and power is acted on；The nanometer primary particle is closely locked in the master by the chemical bond
In the pore structure of conductive network.Shell structure refers to the general clad of negative material, and the predominantly material such as pitch coats, is carbonized
Arrive, therefore the present invention is not set forth in detail.
The key classification made a concerted effort as a kind of improvement of anode material for lithium-ion batteries of the present invention there is provided the strong bond is hydrogen bond
Or/and chemical bond；The oxygen-containing functional group quality for constituting the hydrogen bond or/and chemical bond accounts for whole leading electric network architecture quality
1%~40%.
Improve, the leading electric network has pliability, dominate as one kind of anode material for lithium-ion batteries of the present invention
Contain functional group inside electric network；The hydrogen bond or/and chemical bond inside the leading electric network oxygen-containing functional group reaction and
Obtain.
Improved as one kind of anode material for lithium-ion batteries of the present invention, the leading electric network structure is opening graphene
At least one of structure, opening intumesced graphite structure, quasiflake graphite alkene structure；The primary particle include nanometer lithium from
Sub- anode particle；Between the leading electric network and the primary particle, guidance electric network can also be distributed with, it is described auxiliary
The leading electric network is closely joined together by conductive network with the nanometer primary particle.
Improved as one kind of anode material for lithium-ion batteries of the present invention, the guidance electric network is carbonized by high polymer material
Obtain；The high polymer material is obtained by high polymer monomer in-situ polymerization；In the guidance electric network, in addition to conductive black,
At least one of super conductive carbon, Ketjen black, CNT, graphene, acetylene black.
Present invention additionally comprises a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that mainly includes as follows
Step：
Step 1, prepared by presoma：Primary particle is uniformly scattered in solvent, presoma is obtained；
Step 2, prepared by modified leading electric network structure：Leading electric network structure with loose structure is placed in oxidation ring
In border, grafted functional group obtains modified leading electric network structure；
Step 3, fill：Presoma made from step 1 is filled into modified leading electric network structure；
Step 4, remain silent：It is placed under reducing atmosphere, promotes the functional group being grafted in leading electric network structure to react,
Generation strong bond is made a concerted effort, and the pore structure sealing in porous leading electric network structure or part are sealed；
Step 5, the product of step 4 is coated, being carbonized obtains finished product anode material for lithium-ion batteries.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, the primary particle table described in step 1
Face, by being modified, is function dough primary particle, and the functional group is carboxyl or/and hydroxyl；The functional group being grafted described in step 2
Including at least one of carboxyl, hydroxyl, epoxy radicals, carbonyl, nitro, amino；Reducing environment described in step 4 includes addition and reduced
Agent or/and Direct Hydrothermal reduction.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, polymerization can also be added in step 1
Thing monomer, i.e., mediate after mixing by primary particle, polymer monomer, obtain polymer monomer and be uniformly scattered in nanometer once
The presoma on grain surface；At this time, it may be necessary to carry out polymerisation after step 3, the polymerisation be by the product of step 3,
In the environment for being placed in initiator presence, promote to be scattered in the polymer monomer polymerization on primary particle surface, obtain high molecular polymerization
Thing.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, high score has been additionally added when mediating reaction
Sub- polymer, carbon source component, conductive agent component, solvent composition；Now kneading process described in step 1 is：By nanometer primary particle,
Surfactant 1, polymer monomer, solvent 1 are mediated, and obtain mixture 1；Conductive agent component, surfactant 2, solvent 2 are pinched
Close, obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and obtains precursor pulp.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, the filling process described in step 3 is：
Porous leading electric network structural material is pre-processed, the pretreatment includes surface active or/and addition surface
Activating agent；
Before filling, porous leading electric network structural material is placed in vacuum environment and vacuumized, excluded in pore structure
Air, is the filling vacating space of presoma, is placed in afterwards in precursor pulp and starts filling；
In filling process, apply pressure, presoma is squeezed into hole；Temperature is improved, the viscosity of presoma is reduced；
Increase mechanical disturbance, open hole mouthful.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, polymer monomer bag described in step 1
Include esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol dimethacrylate,
Polyethyleneglycol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl methacrylate, N, N-
DMAA, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate, positive Hexyl 2-propenoate, 2-
Cyclohexyl acrylate, dodecyl acrylate, GDMA, polyethylene glycol dimethacrylate, poly- second two
Alcohol dimethylacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, tetraethylene glycol diacrylate, two
Contracting tripropylene glycol diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythritol acrylate, double-three hydroxyls
Base tetraacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate, glycerol propoxylate 3 third
Olefin(e) acid ester, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylates, propoxylation trihydroxy methyl
Propane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate,
At least one of ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate；Initiator described in step 4
Isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, mistake
Aoxidize the special butyl ester of lauroyl, perbenzoic acid, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, peroxidating
At least one of two dicyclohexyl carbonates.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, height can also be added when mediating reaction
Molecularly Imprinted Polymer, carbon source component, conductive agent component or/and solvent composition, the high molecular polymer include polymethylacrylic acid
In methyl esters (PMMA), Kynoar (PVDF), butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), polypropylene fine (PAN)
At least one, described carbon source component include glucose, sucrose, soluble starch, cyclodextrin, furfural, sucrose, glucose, jade
Rice starch, tapioca, wheaten starch, cellulose, polyvinyl alcohol, polyethylene glycol, Tissuemat E, phenolic resin, vinylpyridine
Pyrrolidone, epoxy resin, polyvinyl chloride, glycan alcohol, furane resins, Lauxite, polymethyl methacrylate, Kynoar
Or at least one of polyacrylonitrile, petroleum coke, oil system needle coke, coal-based needle coke, the conductive agent component include conductive black,
At least one of super conductive carbon, Ketjen black, CNT, graphene, acetylene black, water, alcohols, ketone, alkanes, esters,
At least one in aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran
Kind.
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, electric network knot is dominated described in step 2
Structure preparation process includes：It is prepared by graphene-structured, opening intumesced graphite structure and the quasiflake graphite alkene structure of being open：With scale stone
Ink or micro crystal graphite (can prepare quasiflake graphite alkene, change and be closely joined together between graphene sheet layer, while lamella
Between branch have prosperity gap structure, be easy to the filling of primary particle；Micro crystal graphite alkene particle size is smaller simultaneously, is prepared into
The quasiflake graphite alkene particle diameter arrived is 10 μm or so, is matched very much with final finished lithium ion cell positive particle diameter) it is original
Material, (main oxygenerating degree is moderate, and degree of oxidation is too low, it is impossible to form loose structure for control oxidation intercalation degree；Aoxidize journey
Spend graphite flake layer in height, reduction process and will be completely exfoliated and come, it is impossible to form the loose structure linked together), Zhi Houre
Processing is expanded, you can obtain the loose structure that lamella between same coccolith ink links together, is open between lamella and lamella；It
Obtain modified leading electric network structure as grafted functional group in oxidation environment again afterwards
Improved as one kind of method for preparing anode material of lithium-ion battery of the present invention, the surfactant 1 includes profit
At least one of humectant, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent；The solvent 1 be water, alcohols, ketone,
Alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran
At least one of.The surfactant 2 is included in wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent
It is at least one；The solvent 2 be water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide,
At least one of diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.
The advantage of the invention is that：
1. be modified between leading electric network structure and modified primary particle (or contain polarized on modified leading electric network
Functional group, and metal oxide has polarity in itself, it is relative to be easier well mixed and be filled), with similar function
Group, is more beneficial for the presoma of primary particle formation and enters in the pore structure of leading electric network；Being sufficient filling with for pore structure is realized,
Improve proportion of the primary particle in composite ferric lithium phosphate material；
2. stronger bonding action power, effectively can seal primary particle between leading electric network inside configuration lamella
In leading electric network inside configuration, it is ensured that stability of the primary particle in finished product second particle structure；Meanwhile, dominate electric network
After sealing structure, the contact between electrolyte and primary particle can be effectively obstructed, is decreased or even eliminated in charge and discharge process
The generation of aerogenesis side reaction, so as to improve the cycle performance of battery；
3. teaching electric network structure to be closely connected leading electric network structure with primary particle, increase primary particle is with dominating
Contact area between electric network, reduces contact resistance, and the battery of the anode material for lithium-ion batteries assembling prepared has
Lower impedance；
4. in preparation process, using the low polymer monomer of viscosity and nanometer primary particle mediate and disperse, can be true
Protect nanometer primary particle dispersed, and polymer monomer is uniformly distributed in a nanometer primary particle surface；
5. the presoma with more low viscosity (because polymer monomer viscosity is low), it is easier to be filled into leading electric network
Pore structure in, it is ensured that fill up a nanometer primary particle in the hole of the loose structure of leading electric network.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the embodiment party of the present invention
Formula not limited to this.
Comparative example, prepares the LiFePO4 second particle material that particle diameter is 10 μm；
Step 1, mix：By LiFePO4, conductive black, lauryl sodium sulfate, the polyvinyl pyrrole that particle diameter is 100nm
Alkanone using (mass ratio as:LiFePO4:Conductive black:Lauryl sodium sulfate:Polyvinylpyrrolidone=94:4.9:1:
0.1) and NMP (solid content is 0.5%) mix 10h, obtain slurry.
Step 2, prepared by second particle：Adjustable spraying drying condition, prepares the LiFePO4 that particle diameter is 10 μm
Second particle；Coated afterwards, being carbonized obtains finished product anode material for lithium-ion batteries.
Embodiment 1, is that the present embodiment comprises the following steps with comparative example difference：
Step 1, prepared by presoma：By LiFePO4, methyl methacrylate, the dodecyl sulphate that particle diameter is 100nm
(mass ratio is LiFePO4 to sodium:Methyl methacrylate：Lauryl sodium sulfate=95:4:1), (solid content after NMP mixing
10%) to mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma；
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 1% functional group
Modified quasiflake graphite alkene is stand-by；
Step 3, fill：The modification quasiflake graphite alkene that step 2 is obtained is vacuumized, and the presoma of step 1 is placed in afterwards
In, drive in body apply pressure further along, while ultrasonic vibration so that presoma is inserted in the pore structure of quasiflake graphite alkene, point
From the modification quasiflake graphite alkene for obtaining filling full presoma；
Step 4, polymerisation：The special butyl ester of perbenzoic acid is dissolved in NMP and disperses to obtain solution, step is sprayed onto afterwards
The modification quasiflake graphite alkene surface of the rapid 3 full presomas of obtained filling, heating promotes to be scattered in lithium iron phosphate particles surface
Methyl methacrylate polymerization, so that by lithium iron phosphate particles together with being modified quasiflake graphite alkene lamella and closely bonding；
Step 5, remain silent：The product that step 4 is obtained, carries out solvent thermal reaction, promotes to be grafted on quasiflake graphite alkene piece
Functional group on layer (between adjacent sheets) reacts, and generates new chemical bond, will be sealed at quasiflake graphite alkene lamella opening
Firmly；
Step 6, the product of step 5 is coated to, is carbonized (while by clad and polymer carbonization) and obtains finished product
Anode material for lithium-ion batteries.
Embodiment 2, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 5% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 3, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 15% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 4, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 20% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 5, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 25% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 6, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 40% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 7, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：Particle diameter is mixed for 100nm modified phosphate iron lithium (surface active), CNT, NMP
(solid content is 10%) mediates after conjunction, revolves round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed
Precursor pulp；
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 20% functional group
Modified quasiflake graphite alkene is stand-by；
Step 3, fill：The modification quasiflake graphite alkene that step 2 is obtained is vacuumized, and the presoma of step 1 is placed in afterwards
In, drive in body apply pressure further along, while ultrasonic vibration so that presoma is inserted in quasiflake graphite alkene pore structure, separation
Obtain filling the modification quasiflake graphite alkene of full presoma；
Step 4, remain silent：The product that step 3 is obtained, carries out solvent thermal reaction, promotes to be grafted on quasiflake graphite alkene piece
Functional group on layer (between adjacent sheets) reacts, and generates new chemical bond, will be sealed at quasiflake graphite alkene lamella opening
Firmly；
Step 5, the product of step 4 is coated to, is carbonized (while by clad and polymer carbonization) and obtains finished product
Anode material for lithium-ion batteries.
Remaining is same as Example 1, repeats no more.
Embodiment 8, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：By LiFePO4+100nm cobalt acid lithiums that particle diameter is 100nm, (mass ratio is LiFePO4:Cobalt acid
Lithium=9:1), (mass ratio is (phosphoric acid for trimethylol-propane trimethacrylate, hexadecyldimethyl benzyl ammonium allyl ammonium chloride
Iron lithium+cobalt acid lithium):Trimethylol-propane trimethacrylate:Hexadecyldimethyl benzyl ammonium allyl ammonium chloride=90:4:1)、
(solid content is 10%) mediates after ethanol mixing, revolves round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture
1；By methylvinyldimethoxysilane, graphene, polyoxyethylated alkyl phenol, (mass ratio is methyl ethylene dimethoxy
Silane:Graphene:Polyoxyethylated alkyl phenol=5:4.9:0.1) and after ethanol mixing (solid content is 4%) mediates, and revolves round the sun as 5
Turn/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2 (mass ratio for (LiFePO4+
Cobalt acid lithium):Graphene=90:4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate
Polymer monomer is obtained after 6h and is uniformly wrapped on primary particle (LiFePO4 and cobalt acid lithium) surface, polymer monomer and graphene
Dispersed, graphene and the dispersed presoma of primary particle；
Step 2, modified expanded graphite is dominated electric network structure and prepared：Selection crystalline flake graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, expanded graphite is thermally treated resulting in afterwards；Expanded graphite is placed in dense
It is modified in sulfuric acid, potassium permanganate, the mixture of sodium nitrate, obtains being grafted with the modified expanded graphite of 20% functional group
Leading electric network structure is stand-by；
Step 3, fill：The modified expanded graphite that step 2 is obtained is dominated electric network structure and vacuumized, and step is placed in afterwards
In 1 presoma, drive in body apply pressure further along, while ultrasonic vibration so that presoma is inserted modified expanded graphite and dominated
In electric network pore structure, the modified expanded graphite of the isolated full presoma of filling dominates electric network structure；
Step 4, polymerisation：The special butyl ester of perbenzoic acid is dissolved in NMP and disperses to obtain solution, step is sprayed onto afterwards
The modified expanded graphite surface of the rapid 3 full presomas of obtained filling, heating promotes to be scattered in the metering system on primary particle surface
Sour methyl esters polymerization, so that together with primary particle is closely bonded with modified expanded graphite lamella；
Step 5, remain silent：Reducing agent is added in the product obtained to step 4, promotes to be grafted on modified expanded graphite lamella
Functional group in (between adjacent sheets) reacts, and generates new chemical bond, will be sealed at modified expanded graphite lamella opening；
Remaining is same as Example 1, repeats no more.
Embodiment 9, difference from Example 4 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：It is 100nm nickel cobalt manganese (NCM), methyl methacrylate, dodecyl sulphur by particle diameter
(mass ratio is nickel cobalt manganese to sour sodium:Methyl methacrylate：Lauryl sodium sulfate=95:4:1), (solid content after NMP mixing
10%) to mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma；
Step 2, modified quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 20% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 4, repeats no more.
Battery is assembled：The positive electrode and conductive agent, bonding agent, stirring solvent that comparative example, each embodiment are prepared
Electrode slurry is obtained, applies form anode electrode on a current collector afterwards；By anode electrode, (graphite is active matter with negative electrode
Matter), barrier film assembling obtain naked battery core, bag entered afterwards carry out top side seal, drying, fluid injection, standing, chemical conversion, shaping, degasification to obtain
Resultant battery.
Material properties test：
Gram volume is tested：Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment
Battery core carries out gram volume test：Stand 3min；0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C；Stand 3min；
0.2C constant-current discharges obtain discharge capacity D1 to 3.0V；Stand 3min；0.2C constant-current discharges are to 3.85V；It is complete after standing 3min
Into volume test, the weight of silicon carbon material, that is, obtain negative pole gram volume, acquired results are shown in Table 1 in D1 divided by negative electricity pole piece.
Inner walkway：LiFePO 4 material in each embodiment and comparative example is prepared into by following flow in 25 DEG C of environment
The battery core arrived carries out inner walkway：Stand 3min；1C constant-current charges are to 3.85V, 3.85V constant-voltage charges to 0.1C；Stand 3min；
Electrochemical workstation is used again, the DCR values of battery core are tested, and acquired results are shown in Table 1.
High rate performance is tested：Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment
Battery core carry out high rate performance test：Stand 3min；0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C；Stand
3min；0.2C constant-current discharges obtain discharge capacity D1 to 3.0V；Stand 3min；0.2C constant-current charges to 4.2V, 4.2V constant pressures is filled
Electricity is to 0.05C；Stand 3min；2C constant-current discharges obtain discharge capacity D21 to 3.0V；Stand 3min；High rate performance is completed afterwards
Test, battery high rate performance=D2/D1*100%, acquired results are shown in Table 1.
Loop test:The electricity prepared in 25 DEG C of environment by following flow to each embodiment and comparative example silicon carbon material
Core carries out loop test：Stand 3min；0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C；Stand 3min；0.2C
Constant-current discharge obtains discharge capacity D1 to 3.0V；3min is stood, " 0.2C constant-current charges to 4.2V, 4.2V constant-voltage charges are extremely
0.05C；Stand 3min；0.2C constant-current discharges obtain discharge capacity Di to 3.0V；3min " is stood to repeat to obtain D300 299 times,
Loop test is completed afterwards, and calculating capability retention is D300/D1*100%, and acquired results are shown in Table 1.
It can be obtained by table 1, the present invention can prepare the anode material for lithium-ion batteries of function admirable, with the lithium-ion electric
Pond positive electrode is that the battery core that positive active material assembling is obtained has excellent chemical property.Specifically, comparative examples
It can be obtained with embodiment 1- embodiments 6, with the increase of the oxygen-containing functional group on modified leading electric network frame sheet, the electricity of battery core
Chemical property first improves, and rear to be deteriorated, when this is due to that oxygen-containing functional group is very few, sealing effect is poor, it is impossible to play a role completely；And
When oxygen-containing functional group is excessive, seal too tight, hinder the ion diffusion in charge and discharge process.It can be obtained by each embodiment,
The present invention suitable for energy storage research field, institute's primary particle pelletizing in need obtain the material of second particle structure, specifically wrap
Include lithium ion anode material, ion cathode material lithium (such as graphite, silicon-carbon, LiFePO4, alloy anode) and other electricity
Pond capacitor material (such as lithium-air battery, fuel cell, sodium-ion battery, Zinc ion battery).
The battery core performance table that table 1, different anode material for lithium-ion batteries are prepared
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art exist
Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of the present invention.This
Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Constitute any limitation.
Claims (10)
1. a kind of anode material for lithium-ion batteries, including nuclear structure and shell structure, it is characterised in that the nuclear structure is secondary
Kernel structure, and including the leading electric network with loose structure and be filled in the pore structure of the leading electric network
Nanometer primary particle；The nanometer primary particle includes class lithium cobaltate by nm, nanometer lithium manganate, nano-grade lithium iron phosphate, nanometer nickel-cobalt
At least one of manganese, nanometer nickel-cobalt aluminium, nanometer lithium nickelate, nanometer lithium-barium oxide, nanometer lithium-rich anode material；It is described leading
There is stronger bonding force between electric network to act on；And the nanometer primary particle is closely locked by the bonding force
In the pore structure of the leading electric network.
2. the anode material for lithium-ion batteries described in a kind of claim 1, it is characterised in that the classification for the key that strong bond is made a concerted effort is provided
For hydrogen bond or/and chemical bond；The quality for constituting the oxygen-containing functional group of the hydrogen bond or/and chemical bond accounts for whole leading electric network
The 1%~40% of quality.
3. the anode material for lithium-ion batteries described in a kind of claim 1, it is characterised in that the leading electric network has flexible
Property, and contain functional group inside the leading electric network；The hydrogen bond or/and chemical bond containing inside the leading electric network
Oxygen functional group reactionses and obtain.
4. the anode material for lithium-ion batteries described in a kind of claim 1, it is characterised in that the leading electric network is opening stone
At least one of black alkene structure, opening intumesced graphite structure, quasiflake graphite alkene structure；The nanometer primary particle includes
Nano-lithium ion cell positive electrode particle；Guidance electric network, institute is also distributed between the leading electric network and the primary particle
Guidance electric network is stated to be closely joined together the leading electric network with the nanometer primary particle.
5. the anode material for lithium-ion batteries described in a kind of claim 1, it is characterised in that the guidance electric network is by macromolecule
Material carbonization is obtained；The high polymer material is obtained by high polymer monomer in-situ polymerization；In the guidance electric network, in addition to lead
At least one of electric carbon black, super conductive carbon, Ketjen black, CNT, graphene, acetylene black.
6. the preparation method of the anode material for lithium-ion batteries described in a kind of claim 1, it is characterised in that mainly include as follows
Step：
Step 1, prepared by presoma：Primary particle is uniformly scattered in solvent, presoma is obtained；
Step 2, prepared by modified leading electric network structure：Leading electric network structure with loose structure is placed in oxidation environment
In, grafted functional group obtains modified leading electric network structure；
Step 3, fill：Presoma made from step 1 is filled into modified leading electric network structure；
Step 4, remain silent：It is placed under reducing atmosphere, promotes the functional group being grafted in leading electric network structure to react, generates
Strong bond is made a concerted effort, and the pore structure sealing in porous leading electric network structure or part are sealed；
Step 5, the product of step 4 is coated, being carbonized obtains finished product anode material for lithium-ion batteries.
7. the preparation method of the anode material for lithium-ion batteries described in a kind of claim 6, it is characterised in that described in step 1
Primary particle surface turns into functional group's primary particle by modified, and the functional group is carboxyl or/and hydroxyl；Described in step 2
The functional group of grafting includes at least one of carboxyl, hydroxyl, epoxy radicals, carbonyl, nitro, amino；Reducing environment described in step 4
Including addition reducing agent or/and Direct Hydrothermal reduction.
8. the preparation method of the anode material for lithium-ion batteries described in a kind of claim 6, it is characterised in that also add in step 1
Added with polymer monomer, i.e., mediated after mixing primary particle, polymer monomer, obtain polymer monomer and be uniformly scattered in receive
The presoma on rice primary particle surface；At this time, it may be necessary to carry out polymerisation after step 3, the polymerisation is by step 3
Product, in the environment for being placed in initiator presence, promote to be scattered in the polymer monomer polymerization on primary particle surface, obtain high score
Sub- polymer.
9. the preparation method of the anode material for lithium-ion batteries described in a kind of claim 8, it is characterised in that gone back when mediating reaction
Addition has high molecular polymer, carbon source component, conductive agent component, solvent composition；Now kneading process described in step 1 is：It will receive
Rice primary particle, surfactant 1, polymer monomer, solvent 1 are mediated, and obtain mixture 1；By conductive agent component, surface-active
Agent 2, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and obtains precursor pulp.
10. the preparation method of the anode material for lithium-ion batteries described in a kind of claim 6, it is characterised in that described in step 3
Filling process is：
Porous leading electric network structural material is pre-processed, the pretreatment includes surface active or/and addition surface-active
Agent；
Before filling, porous leading electric network structural material is placed in vacuum environment and vacuumized, the air in discharge pore structure,
For the filling vacating space of presoma, it is placed in afterwards in precursor pulp and starts filling；
In filling process, apply pressure, presoma is squeezed into hole；Temperature is improved, the viscosity of presoma is reduced；Increase
Mechanical disturbance, opens hole mouthful.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634205A (en) * | 2017-09-12 | 2018-01-26 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN107658464A (en) * | 2017-10-31 | 2018-02-02 | 湖南国盛石墨科技有限公司 | Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery |
| CN107742714A (en) * | 2017-10-31 | 2018-02-27 | 湖南国盛石墨科技有限公司 | Preparation method for LiFePO4/expansion micro crystal graphite/carbon composite of lithium ion battery |
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| CN109546086A (en) * | 2018-11-29 | 2019-03-29 | 瑞红锂电池材料(苏州)有限公司 | It is a kind of to lead iron phosphate lithium positive pole pole piece of lithium binder and preparation method thereof using high glue |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901898A (en) * | 2009-12-07 | 2010-12-01 | 耿世达 | Lithium battery LiFePO4 anode material with internal three-dimensional conductive structure and preparation method thereof |
| CN101944593A (en) * | 2010-09-15 | 2011-01-12 | 天津大学 | Positive pole material of lithium ion battery with nanometer structure and preparation method thereof |
| CN103560235A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Graphene-coated sulfur/porous carbon composite positive electrode material and preparation method thereof |
| CN104064738A (en) * | 2014-06-27 | 2014-09-24 | 哈尔滨工业大学 | Hydrothermal preparation method of graphene-coated sulfur/porous carbon composite positive electrode material |
| CN104779395A (en) * | 2015-05-11 | 2015-07-15 | 德阳威旭锂电科技有限责任公司 | Lithium iron phosphate anode materials of three-dimensional conductive network structure and preparation method thereof |
| US20150325850A1 (en) * | 2014-05-08 | 2015-11-12 | Hyundai Motor Comapny | Secondary battery comprising sulfur particle having core-shell structure |
-
2017
- 2017-05-27 CN CN201710391348.1A patent/CN107104227B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901898A (en) * | 2009-12-07 | 2010-12-01 | 耿世达 | Lithium battery LiFePO4 anode material with internal three-dimensional conductive structure and preparation method thereof |
| CN101944593A (en) * | 2010-09-15 | 2011-01-12 | 天津大学 | Positive pole material of lithium ion battery with nanometer structure and preparation method thereof |
| CN103560235A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Graphene-coated sulfur/porous carbon composite positive electrode material and preparation method thereof |
| US20150325850A1 (en) * | 2014-05-08 | 2015-11-12 | Hyundai Motor Comapny | Secondary battery comprising sulfur particle having core-shell structure |
| CN104064738A (en) * | 2014-06-27 | 2014-09-24 | 哈尔滨工业大学 | Hydrothermal preparation method of graphene-coated sulfur/porous carbon composite positive electrode material |
| CN104779395A (en) * | 2015-05-11 | 2015-07-15 | 德阳威旭锂电科技有限责任公司 | Lithium iron phosphate anode materials of three-dimensional conductive network structure and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634205A (en) * | 2017-09-12 | 2018-01-26 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN107658464A (en) * | 2017-10-31 | 2018-02-02 | 湖南国盛石墨科技有限公司 | Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery |
| CN107742714A (en) * | 2017-10-31 | 2018-02-27 | 湖南国盛石墨科技有限公司 | Preparation method for LiFePO4/expansion micro crystal graphite/carbon composite of lithium ion battery |
| CN107799753A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of method that phosphoric acid vanadium lithium/expansion micro crystal graphite combination electrode material is prepared in Metal Substrate |
| CN109546086A (en) * | 2018-11-29 | 2019-03-29 | 瑞红锂电池材料(苏州)有限公司 | It is a kind of to lead iron phosphate lithium positive pole pole piece of lithium binder and preparation method thereof using high glue |
| CN109546086B (en) * | 2018-11-29 | 2020-09-29 | 瑞红锂电池材料(苏州)有限公司 | Lithium iron phosphate positive pole piece using high-viscosity lithium binder and preparation method thereof |
| CN110620237A (en) * | 2019-10-25 | 2019-12-27 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN113707879A (en) * | 2021-07-27 | 2021-11-26 | 深圳市先进石墨烯科技有限公司 | Composite cathode material, preparation method thereof and lithium ion battery |
| CN115172718A (en) * | 2022-08-01 | 2022-10-11 | 湖北万润新能源科技股份有限公司 | Method for preparing lithium iron manganese phosphate by solid-phase coating method |
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