CN107180956A - Lithium titanate anode material and preparation method thereof - Google Patents
Lithium titanate anode material and preparation method thereof Download PDFInfo
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- CN107180956A CN107180956A CN201710391330.1A CN201710391330A CN107180956A CN 107180956 A CN107180956 A CN 107180956A CN 201710391330 A CN201710391330 A CN 201710391330A CN 107180956 A CN107180956 A CN 107180956A
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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
- H01M4/362—Composites
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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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- 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
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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
- H01M4/485—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to energy storage research field, more particularly to a kind of lithium titanate anode material, 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；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 lithium titanate anode material has excellent chemical property.
Description
Technical field
The invention belongs to energy storage material technical field, more particularly to a kind of lithium titanate anode material and preparation method thereof.
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：More quick discharge and recharge (such as 5C even 10C), (such as subzero 30 is Celsius for broader temperature range
Degree) in use；The more excellent electrode material of new performance is had to look for solve the above problems.
Current commercialized lithium ion battery negative material is mainly graphite, but because of slow (the general charge and discharge of its charge/discharge rates
Electric speed is within 1C), and cryogenic property is poor (temperature in use is typically more than -10 DEG C), and the urgent of user can not be met
Demand；Therefore, more high charge-discharge speed, the negative material used in more wide temperature range exploitation it is extremely urgent.As lithium from
Sub- cell negative electrode material, lithium titanate receives much concern always：Its charge/discharge rates can be remained able in more than 10C, and at -30 DEG C
Ideal capacity has been given play to, therefore has been that one of optimal selection of negative material is filled soon by a new generation.
But it is due to that lithium titanate material particle electric conductivity itself is poor, it is larger to be assembled into the internal resistance of battery after battery, and
In charge and discharge process, easily produce gas to influence the use of battery, limit it and widely apply.It is above-mentioned in order to solve
Problem, prior art mainly has lithium titanate particle nanosizing, added into lithium titanate material particle with excellent conductive capability
Conductive material etc., to improve the electric conductivity of lithium titanate material integral particle；Coating technology is used simultaneously, is reduced material and is prepared
Aerogenesis problem during being reused after into battery.
But the lithium titanate particle of nanostructured is easily reunited, disperse difficulty big；And conventional conductive agent material, usual chi
Very little smaller (nanoscale), and specific surface area is larger, scattered difficulty is bigger.But when, to maximize the conductive effect of conductive agent with
And the more excellent lithium titanate second particle material of processability, it is necessary to ensure that nano lithium titanate particle uniformly divides with conductive agent
Dissipate.Meanwhile, contact area between nanostructured metatitanic acid lithium material and conductive agent is smaller, gap is larger, therefore contact resistance phase
To it is larger, easily with electrolyte contacts produce gas, the internal resistance of cell for preparing is higher, gas production is bigger during use,
So as to influence the chemical property of lithium titanate anode material.
In view of this, it is necessory to propose a kind of lithium titanate anode material and preparation method thereof, it can be scattered by two kinds
The larger material (nano lithium titanate particle, conductive network) of difficulty is dispersed, while ensuring to be close-coupled between the two
Together, so as to prepare the lithium titanate anode material 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 lithium titanate anode material provided, including core
Structure and shell structure, the nuclear structure are 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；Exist between the leading network structure stronger
Chemical bond and power effect；The nanometer primary particle is closely locked in the pore structure of the leading electric network by the chemical bond
In.So that it is guaranteed that the lithium titanate anode material has excellent chemical property.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of lithium titanate anode material, including nuclear structure and shell structure, the nuclear structure are second particle structure, and wherein
Including the leading electric network with loose structure and the nanometer being filled in the porous leading electric network pore structure once
Grain；There is stronger chemical bond between the leading network structure and power is acted on；The chemical bond is by the nanometer primary particle
In the pore structure for being closely locked in the leading electric network, contain lithium titanate particle in the nanometer primary particle.Shell structure
Refer to the general clad of negative material, the predominantly material such as pitch cladding, carbonization is obtained, therefore the present invention does not do and explained in detail
State.
The key classification made a concerted effort there is provided the strong bond as a kind of improvement of lithium titanate anode material of the present invention for hydrogen bond or/
And chemical bond；The oxygen-containing functional group quality for constituting the hydrogen bond or/and chemical bond accounts for the 1% of whole leading electric network architecture quality
~40%.
Improved as one kind of lithium titanate anode material of the present invention, the leading electric network has pliability, dominate power network
Contain functional group inside network；The hydrogen bond or/and the chemical bond oxygen-containing functional group inside the leading electric network react and obtained.
Improved as one kind of lithium titanate anode material of the present invention, the leading electric network structure is opening graphene knot
At least one of structure, opening intumesced graphite structure, quasiflake graphite alkene structure；The primary particle includes nano lithium titanate
Negative pole particle；Between the leading electric network and the primary particle, guidance electric network, the guidance power network can also be distributed with
The leading electric network is closely joined together by network with the nanometer primary particle.
Improved as one kind of lithium titanate anode material of the present invention, the nanometer primary particle also includes non-nano lithium titanate
Negative pole particle；The non-nano lithium titanate anode particle be native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon,
Petroleum coke, carbon fiber, thermal decomposed resins carbon, silicon-carbon cathode particle, tin base cathode material, transition metal nitride, kamash alloy, germanium
At least one of based alloy, acieral, antimony-containing alloy, magnesium base alloy；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 lithium titanate anode material, it is characterised in that mainly comprises the following steps：
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 lithium titanate anode material.
Improved as one kind of lithium titanate anode material preparation method of the present invention, the primary particle surface warp described in step 1
Cross modified, be function dough primary particle, the functional group is carboxyl or/and hydroxyl；The functional group being grafted described in step 2 includes
At least one of carboxyl, hydroxyl, epoxy radicals, carbonyl, nitro, amino；Reducing environment described in step 4 includes addition reducing agent
Or/and Direct Hydrothermal reduction.
Improved as one kind of lithium titanate anode material preparation method of the present invention, polymer list can also be added in step 1
Body, i.e., mediate after mixing primary particle, polymer monomer, obtain polymer monomer and be uniformly scattered in a nanometer primary particle table
The presoma in face；At this time, it may be necessary to carry out polymerisation after step 3, the polymerisation is, by the product of step 3, to be placed in
In the environment that initiator is present, promote to be scattered in the polymer monomer polymerization on primary particle surface, obtain high molecular polymer.
Improve, wrapped in nanometer primary particle described in step 1 as one kind of lithium titanate anode material preparation method of the present invention
Contain nano lithium titanate particle；Non-nano lithium titanate anode particle can also be included in the nanometer primary particle；Mediate reaction
When be additionally added high molecular polymer, carbon source component, conductive agent component, solvent composition；Now kneading process described in step 1 is：
Nanometer primary particle, surfactant 1, polymer monomer, solvent 1 are mediated, mixture 1 is obtained；By conductive agent component, surface
Activating agent 2, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and obtains forerunner's somaplasm
Material.
Improved as one kind of lithium titanate anode material preparation method 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 lithium titanate anode material preparation method of the present invention, polymer monomer described in step 1 includes third
Olefin(e) acid esters, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol dimethacrylate, poly- second
Omega-diol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl methacrylate, N, N- diformazans
Base acrylamide, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate, positive Hexyl 2-propenoate, 2- propylene
Sour cyclohexyl, dodecyl acrylate, GDMA, polyethylene glycol dimethacrylate, polyethylene glycol two
Methacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, tetraethylene glycol diacrylate, two contractings three
Propylene glycol diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythritol acrylate, double-trihydroxy third
Alkane tetraacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate, the acrylic acid of glycerol propoxylate three
Ester, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylates, propoxylation trimethylolpropane
Triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxy
At least one of base trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate；Initiator isopropyl described in step 4
Benzene hydrogen peroxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, peroxidating
The special butyl ester of lauroyl, perbenzoic acid, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, the carbon of peroxidating two
At least one of sour dicyclohexyl maleate.
Improve, wrapped in nanometer primary particle described in step 1 as one kind of lithium titanate anode material preparation method of the present invention
Contain nano lithium titanate particle；Non-nano lithium titanate anode particle can also be included in the nanometer primary particle, it is described non-to receive
Rice lithium titanate anode particle is native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, pyrolysis
Resin carbon, silicon-based anode particle, tin base cathode material, transition metal nitride, kamash alloy, germanium-base alloy, acieral, antimony
At least one of based alloy, magnesium base alloy；High molecular polymer, carbon source component, conductive agent can also be added when mediating reaction
Component or/and solvent composition, the high molecular polymer include polymethyl methacrylate (PMMA), Kynoar
(PVDF), at least one of butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), polypropylene fine (PAN), the carbon source group
Dividing includes glucose, sucrose, soluble starch, cyclodextrin, furfural, sucrose, glucose, cornstarch, tapioca, wheat shallow lake
Powder, cellulose, polyvinyl alcohol, polyethylene glycol, Tissuemat E, phenolic resin, vinyl pyrrolidone, epoxy resin, polychlorostyrene second
Alkene, glycan alcohol, furane resins, Lauxite, polymethyl methacrylate, Kynoar or polyacrylonitrile, petroleum coke, oil system
At least one of needle coke, coal-based needle coke, the conductive agent component include conductive black, super conductive carbon, Ketjen black, carbon and received
At least one of mitron, graphene, acetylene black, water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE,
At least one of dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.
Improved as one kind of lithium titanate anode material preparation method of the present invention, electric network structure system is dominated described in step 2
Standby process includes：It is prepared by graphene-structured, opening intumesced graphite structure and the quasiflake graphite alkene structure of being open：With crystalline flake graphite or
Micro crystal graphite (can prepare quasiflake graphite alkene, change and be closely joined together between graphene sheet layer, while between lamella
There is the gap structure of prosperity in branch, is easy to the filling of primary particle；Micro crystal graphite alkene particle size is smaller simultaneously, prepares
Quasiflake graphite alkene particle diameter is 10 μm or so, is matched very much with final finished lithium titanate anode particle diameter) it is raw material, control oxygen
Changing intercalation degree, (main oxygenerating degree is moderate, and degree of oxidation is too low, it is impossible to form loose structure；Degree of oxidation is too high, also
Graphite flake layer will be completely exfoliated and come during original, it is impossible to form the loose structure that links together), be heat-treated afterwards it is expanded,
It can obtain the loose structure that lamella between same coccolith ink links together, is open between lamella and lamella；Afterwards again as
Grafted functional group in oxidation environment, obtains modified leading electric network structure
As lithium titanate anode material preparation method of the present invention one kind improve, the surfactant 1 comprising wetting agent,
At least one of dispersant, bleeding agent, solubilizer, cosolvent, cosolvent；The solvent 1 be water, alcohols, ketone, alkanes,
In esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran extremely
Few one kind.The surfactant 2 includes at least one in wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent
Kind；The solvent 2 is water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethyl
At least one of formamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.
The advantage of the invention is that：
1. being modified between leading electric network structure and modified primary particle, with similar functional group, it is more beneficial for once
Granuloplastic presoma enters in the pore structure of leading electric network；Being sufficient filling with for pore structure is realized, primary particle is improved and exists
Proportion in lithium titanate composite 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 thoroughly solve the problems, such as the aerogenesis in lithium titanate battery cyclic process；
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 lithium titanate battery 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 lithium titanate second particle material that particle diameter is 10 μm；
Step 1, mix：By lithium titanate, conductive black, lauryl sodium sulfate, the polyvinylpyrrolidine that particle diameter is 100nm
Ketone using (mass ratio as:Lithium titanate:Conductive black:Lauryl sodium sulfate:Polyvinylpyrrolidone=94:4.9:1:0.1) and
NMP (solid content is 0.5%) mixes 10h, obtains slurry.
Step 2, prepared by second particle：Adjustable spraying drying condition, prepares the lithium titanate two that particle diameter is 10 μm
Secondary particle；Coated afterwards, being carbonized obtains finished product lithium titanate anode material.
Embodiment 1, is that the present embodiment comprises the following steps with comparative example difference：
Step 1, prepared by presoma：By lithium titanate, methyl methacrylate, lauryl sodium sulfate of the particle diameter for 100nm
(mass ratio is lithium titanate:Methyl methacrylate：Lauryl sodium sulfate=95:4:1), (solid content is after NMP mixing
10%) 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 the first on lithium titanate particle surface
Base methyl acrylate polymerize, so that by lithium titanate particle 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
Lithium titanate anode material.
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 lithium titanate (surface hydroxylation), 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
Lithium titanate anode material.
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：(mass ratio is lithium titanate to the lithium titanate+Delanium for being 100nm by particle diameter:Delanium=9:
1), (mass ratio is (lithium titanate+artificial for trimethylol-propane trimethacrylate, hexadecyldimethyl benzyl ammonium allyl ammonium chloride
Graphite):Trimethylol-propane trimethacrylate:Hexadecyldimethyl benzyl ammonium allyl ammonium chloride=90:4:1), ethanol is mixed
(solid content is 10%) mediates afterwards, revolves round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By methyl
(mass ratio is methylvinyldimethoxysilane for vinyl dimethoxysilane, graphene, polyoxyethylated alkyl phenol:Stone
Black alkene:Polyoxyethylated alkyl phenol=5:4.9:0.1) and after ethanol mixing (solid content is 4%) mediates, and revolves round the sun as 5 turns/min,
From switching to 10 turns/min；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is (lithium titanate+Delanium):
Graphene=90:4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Obtained after mediating 6h
Polymer monomer is uniformly wrapped on primary particle (lithium titanate and Delanium) surface, polymer monomer and graphene uniform point
Scattered, 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；
Rapid 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 3 full presomas of obtained filling, heating promotes to be scattered in the methacrylic acid on primary particle surface
Methyl esters polymerize, 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.
Battery is assembled：It is lithium titanate anode material and conductive agent that comparative example, embodiment 1- embodiments 8 are prepared, viscous
Connect agent, stirring solvent and obtain electrode slurry, apply form negative electrode on a current collector afterwards；By negative electrode and anode electrode
The assembling of (cobalt acid lithium is active material), barrier film obtains naked battery core, and bag is entered afterwards and carries out top side seal, drying, fluid injection, standing, change
Resultant battery is obtained into, shaping, degasification.
Material properties test：
Gram volume is tested：Lithium titanate 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 gram volume test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand 3min；
1C constant-current discharges obtain discharge capacity D1 to 1.5V；Stand 3min；1C constant-current charges are to 2.35V；Completion is held after standing 3min
The weight of lithium titanate material, that is, obtain negative pole gram volume, acquired results are shown in Table 1 in measurement examination, D1 divided by negative electricity pole piece.
Inner walkway：Lithium titanate material in each embodiment and comparative example is prepared by following flow in 25 DEG C of environment
Battery core carry out inner walkway：Stand 3min；1C constant-current charges are to 2.35V, 2.35V constant-voltage charges to 0.1C；Stand 3min；Again
Using electrochemical workstation, the DCR values of battery core are tested, acquired results are shown in Table 1.
High rate performance is tested：Each embodiment and comparative example lithium titanate material are prepared into by following flow in 25 DEG C of environment
The battery core arrived carries out high rate performance test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand
3min；0.5C constant-current discharges obtain discharge capacity D1 to 1.5V；Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges
To 0.1C；Stand 3min；5C constant-current discharges obtain discharge capacity D2 to 1.5V；Stand 3min；High rate performance is completed afterwards to survey
Examination, battery high rate performance=D2/D1*100%, acquired results are shown in Table 1.
Loop test:Each embodiment and comparative example lithium titanate material are prepared by following flow in 25 DEG C of environment
Battery core carries out loop test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand 3min；1C constant currents
1.5V is discharged to, discharge capacity D1 is obtained；Stand 3min, " 1C constant-current charges to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand
3min；1C constant-current discharges obtain discharge capacity Di to 1.5V；Stand 3min " to repeat to obtain D1000 999 times, circulation is completed afterwards
Test, calculating capability retention is D1000/D1*100%, and acquired results are shown in Table 1.
Gas production is evaluated：The above-mentioned battery outward appearance for finishing loop test of observation, judge its gas production number.It the results are shown in Table
1。
It can be obtained by table 1, the present invention can prepare the lithium titanate anode material of function admirable, with the lithium titanate anode material
Expect that assembling obtained battery core for negative electrode active material has excellent chemical property.Specifically, comparative examples and embodiment
1- embodiments 6 can be obtained, with the increase of the oxygen-containing functional group on modified leading electric network frame sheet, the chemical property of battery core
First improve, 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 as oxygen-containing official
When can roll into a ball excessive, seal too tight, hinder the ion diffusion in charge and discharge process.It can be obtained by each embodiment, present invention tool
There is universality.
The battery core performance table that table 1, different lithium titanate anode materials 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 lithium titanate anode material, including nuclear structure and shell structure, it is characterised in that the nuclear structure is second particle knot
Structure, and including the leading electric network with loose structure and the nanometer being filled in the pore structure of the leading electric network
Primary particle；There is stronger bonding force between the leading electric network to act on；And by the bonding force by the nanometer
Primary particle is closely locked in the pore structure of the leading electric network, and lithium titanate is contained in the nanometer primary particle
Grain.
2. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the classification for providing the key that strong bond is made a concerted effort is hydrogen
Key or/and chemical bond；The quality for constituting the oxygen-containing functional group of the hydrogen bond or/and chemical bond accounts for the quality of whole leading electric network
1%~40%.
3. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the leading electric network has pliability,
And contain functional group inside the leading electric network；The hydrogen bond or/and chemical bond are oxygen-containing inside the leading electric network
Functional group reactionses and obtain.
4. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the leading electric network is opening graphene
At least one of structure, opening intumesced graphite structure, quasiflake graphite alkene structure；The nanometer primary particle includes nanometer
Lithium titanate anode particle；Guidance electric network, the guidance electricity are also distributed between the leading electric network and the primary particle
The leading electric network is closely joined together by network with the nanometer primary particle.
5. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the nanometer primary particle also includes non-receive
Rice lithium titanate anode particle；The non-nano lithium titanate anode particle is native graphite, Delanium, carbonaceous mesophase spherules, soft
Carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, silicon-carbon cathode particle, tin base cathode material, transition metal nitride, tin
At least one of based alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy；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 lithium titanate anode material described in a kind of claim 1, it is characterised in that main to include following step
Suddenly：
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 lithium titanate anode material.
7. the preparation method of the lithium titanate anode material described in a kind of claim 6, it is characterised in that described in step 1 once
Particle surface turns into functional group's primary particle by modified, and the functional group is carboxyl or/and hydroxyl；It is grafted described in step 2
Functional group include at least one of carboxyl, hydroxyl, epoxy radicals, carbonyl, nitro, amino；Reducing environment includes described in step 4
Add reducing agent or/and Direct Hydrothermal reduction.
8. the preparation method of the lithium titanate anode material described in a kind of claim 6, it is characterised in that be also added with step 1
Polymer monomer, i.e., mediate after mixing primary particle, polymer monomer, obtain polymer monomer and be uniformly scattered in nanometer one
The presoma of secondary particle surface；At this time, it may be necessary to carry out polymerisation after step 3, the polymerisation is by the production of step 3
In thing, the environment for being placed in initiator presence, promote to be scattered in the polymer monomer polymerization on primary particle surface, obtain polyphosphazene polymer
Compound.
9. a kind of preparation method of the lithium titanate anode material described in claim 8, it is characterised in that nanometer one described in step 1
Include nano lithium titanate particle in secondary particle；Also include non-nano lithium titanate anode particle in the nanometer primary particle；Pinch
High molecular polymer, carbon source component, conductive agent component, solvent composition have been additionally added when closing reaction；Now mediated described in step 1
Cheng Wei：Nanometer primary particle, surfactant 1, polymer monomer, solvent 1 are mediated, mixture 1 is obtained；By conductive agent group
Divide, surfactant 2, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed before obtaining
Drive somaplasm material.
10. a kind of preparation method of the lithium titanate anode material described in claim 6, it is characterised in that the filling described in step 3
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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| CN109148863A (en) * | 2018-09-03 | 2019-01-04 | 新奥石墨烯技术有限公司 | lithium titanate-graphene composite material and its preparation method and application |
| CN110277543A (en) * | 2018-03-16 | 2019-09-24 | 国家能源投资集团有限责任公司 | Mix negative electrode material and cathode pole piece and preparation method thereof |
| CN112687874A (en) * | 2020-12-28 | 2021-04-20 | 萝北奥星新材料有限公司 | High-stability lithium battery negative electrode material and application thereof |
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