CN107275595A - A kind of lithium titanate anode material and preparation method thereof - Google Patents
A kind of lithium titanate anode material and preparation method thereof Download PDFInfo
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- CN107275595A CN107275595A CN201710392712.6A CN201710392712A CN107275595A CN 107275595 A CN107275595 A CN 107275595A CN 201710392712 A CN201710392712 A CN 201710392712A CN 107275595 A CN107275595 A CN 107275595A
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 shell structure is uniformly wrapped on the nuclear structure surface, the nuclear structure particle diameter is D1, and the shell structure thickness is h1, contains graphene in the shell structure, the graphene is porous graphene, 2≤100nm of the graphene sheet layer thickness h；Pore size distribution$ on the porous graphene lamella is on the graphene film layer plane；The width of continuous part is d1, d1≤π * D1 between the pore structure diameter D2, holes.So as to prepare the lithium titanate anode material of excellent electrochemical performance.
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 or coated on lithium titanate anode material surface, is stablizing material
While expecting structure, moreover it is possible to obstruct lithium titanate material and directly contacted with electrolyte, it is to avoid battery is produced largely in cyclic process
Gas；So as to while cycle performance of battery is improved, solve the problems, such as lithium titanate battery aerogenesis.
Itself it is a kind of excellent covering material because grapheme material has unique flexible two-dimension plane structure,
Lithium titanate anode material surface can be coated on.But its two-dimentional lamellar structure is transmitted to ion inside and outside lithium titanate anode particle
During have obvious inhibition, so as to have influence on the performance of lithium titanate material dynamic performance.
In view of this, it is necessory to propose a kind of lithium titanate anode material and preparation method thereof, it can both give play to graphite
The sharpest edges of alkene, are avoided that it on influenceing transmission of the ion inside and outside lithium titanate material after lithium titanate material Surface coating again.
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 shell structure are uniformly wrapped on the nuclear structure surface, and the nuclear structure particle diameter is D1, the shell
Structural thickness is h1, and graphene is contained in the shell structure, and the graphene is porous graphene, the graphene sheet layer thickness
h2≤100nm；Pore size distribution$ on the porous graphene lamella is on the graphene film layer plane；The pore structure is straight
The width of continuous part is d1, d1≤π * D1 between footpath D2, holes.So as to which the lithium titanate for preparing excellent electrochemical performance is born
Pole material.
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 shell structure are uniformly wrapped on the nuclear structure
Surface, the nuclear structure particle diameter is D1, and the shell structure thickness is h1, and 10nm≤h1≤5 μm, shell is too small, it is impossible to risen
To covered effect, shell is excessive, will hinder ion diffusion；Contain graphene in the shell structure, the graphene is porous stone
Black alkene, 2≤100nm of the graphene sheet layer thickness h；Pore size distribution$ on the porous graphene lamella is in the graphene
In slice plane；Pore structure the diameter D2, D2≤D1；Between holes the width of continuous part be d1, d1≤π * D1, i.e., this
When, the continuum between porous graphene lamella holes at most envelopes the half region of nuclear structure, will not completely enclose
Transmission of the ion inside and outside lithium titanate anode material.
Improved as one kind of lithium titanate anode material of the present invention, the nuclear structure is primary particle structure or second particle
Structure or multiple particle structure；Lithium titanate component is included in the nuclear structure, non-lithium titanate component, the non-titanium can also be included
Sour lithium component particles include native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, pyrolysis tree
At least one of fat carbon, silicon-carbon cathode, alloy material of cathode.
Improved as one kind of lithium titanate anode material of the present invention, the width of continuous part between the porous graphene holes
Spend for the π D1/3 of d1≤2, when graphene coated is on primary particle surface, if d1=2 π D1/3, then ion is by graphene film
Layer edge (or in pore structure) diffuses to path during central area between graphene sheet layer holes, is exactly equal to ion by core knot
Structure diffusion into the surface enters the path of core central area, and now graphene sheet layer influences on the dynamic performance of lithium titanate anode material
It is smaller.
Improved as one kind of lithium titanate anode material of the present invention, in the clad, also include traditional clad or/
The polymer carbonization component obtained with monomer in situ polymerization.
Improved as one kind of lithium titanate anode material of the present invention, traditional clad is traditional clad raw material charing
Obtain；Traditional clad raw material is phenolic resin, melamine resin, Vinylidene Chloride, pitch, polyethylene, stearic acid, PVC, poly-
Acrylonitrile, natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers, polyethylene, polypropylene, polyamide, poly terephthalic acid
In glycol ester, nano cupric oxide, nano magnesia, nano-titanium oxide, nano aluminium oxide, nano-graphite, graphite flake at least
It is a kind of；The monomer includes esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol
Dimethylacrylate, polyethyleneglycol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl
Methyl acrylate, N, N- DMAAs, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate,
Positive Hexyl 2-propenoate, 2- cyclohexyl acrylates, dodecyl acrylate, GDMA, polyethylene glycol dimethyl
It is acrylate, polyethylene glycol dimethacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, four sweet
Alcohol diacrylate, tri (propylene glycol) diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythrite third
Olefin(e) acid ester, double-Glycerin tetraacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate,
Glycerol propoxylate triacrylate, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylates, third
Epoxide trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylation trihydroxy methyl
At least one of propane triacrylate, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate.
Present invention additionally comprises a kind of preparation method of lithium titanate anode material, mainly comprise the following steps：
Step 1, selection nuclear structural materials are standby；
Step 2, the clad slurry containing porous graphene lamella is prepared；
Step 3, nuclear structural materials described in step 1 are placed in the slurry that step 2 is obtained and coated, is carbonized afterwards
Obtain finished product lithium titanate anode material.
Improve, can also be included in the clad slurry as one kind of lithium titanate anode material preparation method of the present invention
Traditional clad raw material or/and polymer monomer.
As lithium titanate anode material preparation method of the present invention one kind improve, when in the clad contain polymer list
During body, after the step 3 cladding process, inducer need to be added and promote monomer in situ polymerization formation polymer, now, step
Three are：Nuclear structural materials described in step 1 are placed in the slurry that step 2 is obtained and coated, is subsequently placed in and is deposited with inducer
Environment in induce monomer in situ polymerization；Finally it is carbonized and obtains finished product lithium titanate anode material.The inducer is
Initiator, the initiator includes isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, the spy of peroxidating two
The special butyl ester of butyl, dibenzoyl peroxide, dilauroyl peroxide, perbenzoic acid, peroxide tert pivalate ester, peroxidating
At least one of two diisopropyl carbonates, di-cyclohexylperoxy di-carbonate.
Improved as one kind of lithium titanate anode material preparation method of the present invention, the preparation described in step 2 contains graphene
During the clad slurry of lamella, surfactant can also be added, the surfactant includes the surface-active
Agent is that surfactant includes at least one of wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent；It is described
Wetting agent is anionic or/and non-ionic wetting agent；The dispersant is fatty acid/aliphatic amide type/esters point
An at least class in powder, paraffin class, metal soap, low molecule wax class, HPMA；The bleeding agent is non-ionic or/and the moon
Ionic bleeding agent；The anionic wetting agents include alkyl sulfate, sulfonate, aliphatic acid or fatty acid ester sulfate,
At least one of carboxylic acid soaps and phosphate；The non-ionic wetting agent includes polyoxyethylated alkyl phenol, polyoxyethylene
At least one of fatty alcohol ether and polyoxyethylene polyoxypropylene block copolymer；The dispersant is vinyl stearic bicine diester
Amine, oleic acid acyl, glyceryl monostearate, glyceryl tristearate, atoleine, microcrystalline wax, barium stearate, zinc stearate,
At least one of calcium stearate, Tissuemat E and polyethylene glycol；The nonionic penetrant includes JFC, JFC-1, JFC-2
At least one of with JFC-E；The anionic bleeding agent comprising fast penetrant T, alkali-resistant penetrant OEP-70, alkaline-resisting ooze
Saturating at least one of agent AEP and seeping at high temperature agent JFC-M；The cosolvent includes benzoic acid, sodium benzoate, salicylic acid, water
At least one of poplar acid sodium, p-aminobenzoic acid, urethane, urea, acid amides, acetamide, borax and KI；It is described latent molten
Agent includes at least one of ethanol, glycerine, propane diols and polyethylene glycol.
Improved as one kind of lithium titanate anode material preparation method of the present invention, nuclear structural materials material described in step 1
The a diameter of D1 of grain, D1 >=1 μm；The width of continuous part is d1≤π * D1 between porous graphene holes described in step 2.
The advantage of the invention is that：
1. flexible, the graphene coated structure of planar structure, it can be coated with significantly more efficient, obstruct electrolyte and core
The direct contact of structure, improves the chemical property of material；
2.d1≤π D1 (smaller scope d1≤2 π D1/3) are the width of continuous part between porous graphene lamella holes
For the half no more than nuclear structure girth, because the graphene of planar structure has inhibition to ion diffusion, but it ought use
During porous graphene of the present invention, ion is smaller around row distance (distance of second particle radius length), therefore hinders to make
With faint, lithium titanate anode material has excellent chemical property；
3. containing small molecule monomer in-situ polymerization component in clad, it can effectively improve each group inside clad and divide it
Between link effect, and the electronic conductance effect between clad and nuclear structure, because small molecule monomer is easier and other
Component infiltration, uniform mixing.
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 anode material that particle diameter is 12 μm；
It is prepared by step 1. nuclear structure：100nm lithium titanate is selected, pelletizing is carried out after uniformly being mixed with conductive agent component, obtains
It is stand-by to the second particle nuclear structure that particle diameter is about 12 μm；
Step 2., as covering material, is coated to the nuclear structure that step 1 is prepared, is carbonized afterwards from pitch,
Obtain the lithium titanate anode material that particle diameter is 12 μm.
Embodiment 1, is that the present embodiment comprises the following steps with comparative example difference：
It is prepared by step 1. nuclear structure：100nm lithium titanate is selected, pelletizing is carried out after uniformly being mixed with conductive agent component, obtains
It is stand-by to the second particle nuclear structure that particle diameter is about 12 μm；
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 1 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 37.68 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain bag
Coating raw material；
Step 3, nuclear structural materials described in step 1 are placed in the clad raw material that step 2 is obtained and coated, it is laggard
Row carbonization obtains finished product lithium titanate anode material.
Embodiment 2, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 1 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 25.12 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain bag
Coating raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 3, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 1 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 15 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain clad
Raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 4, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 1 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 5 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain clad
Raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 5, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 1 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 1 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain clad
Raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 6, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 1 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 0.2 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain cladding
Layer raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 7, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 10 μm, holes by bore dia
Width is uniformly dispersed in nmp solvent for 5 μm of porous graphene, is added afterwards in pitch；It is uniformly mixing to obtain clad
Raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 8, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；It is continuous part between 0.2 μm, holes by bore dia
Width be uniformly dispersed in for 5 μm of porous graphene in nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain cladding
Layer raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 9, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, prepared by nuclear structure：100nm lithium titanate is selected, pelletizing is carried out after uniformly being mixed with conductive agent component, obtains
It is stand-by to the second particle nuclear structure that particle diameter is about 12 μm；
Step 2, clad slurry is prepared：Be 1 μm by trimethylol-propane trimethacrylate and bore dia, holes it
Between the width of continuous part mediated for 5 μm of porous graphene, it is well mixed after；It is well mixed afterwards with phenolic resin
To clad slurry；
Step 3, nuclear structural materials described in step 1 are placed in the clad slurry that step 2 is obtained and coated, it is rearmounted
In BPO solution, promote monomer to carry out in-situ polymerization generation polymer, the polymer of generation by inside clad, clad
It is closely joined together between nuclear structure；Finally it is carbonized and obtains finished product lithium titanate anode material.
It is other identical with comparative example 1, it is not repeated herein.
Embodiment 10, prepares the lithium titanate anode material that particle diameter is 100 μm；
Step 1：Prepared by nuclear structure, selection particle diameter is 200nm lithium titanate, Delanium hybrid particles are as once
Grain, wherein metatitanic acid lithium content are 90%；CNT, super conductive carbon mix are conductive agent component；By detergent alkylate sulphur
Sour sodium, primary particle mixing, add a small amount of N, N- dimethyl pyrrolidone solution is mediated, and obtains primary particle uniform afterwards
Scattered slurry；Conductive agent, PVP are mixed, a small amount of N is added afterwards, N- dimethyl pyrrolidone solution is mediated, and obtains stone
The dispersed slurry of black alkene；Two kinds of slurries are uniformly mixed, pelletizing obtains nuclear structure afterwards；
Step 2, clad slurry is prepared：It is that 100nm, bore dia are continuous part between 1 μm, holes by lamellar spacing
Width for 5 μm porous graphene, PVP, NMP mixing mediated, it is well mixed after；It is well mixed afterwards with phenolic resin
To clad slurry；
It is other identical with comparative example 1, it is not repeated herein.
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。
The battery core chemical property table that table 1, different lithium titanate anode materials are prepared
It can be obtained by table 1, lithium titanate anode material prepared by the present invention, with more outstanding chemical property：It is i.e. higher
Gram volume, more preferable circulation volume conservation rate and higher high rate performance.Specifically, comparative examples are real with embodiment 1-
Applying example 6 can obtain, and with the reduction of the width of continuous part between clad porous graphene holes, the gram volume of material first increases
Plus, it is rear keep stable, DCR is gradually reduced, and cycle performance is first lifted to be declined afterwards, and high rate performance is gradually stepped up, and aerogenesis problem is able to
Solve, because after the width of continuous part reduces between porous graphene holes, it drops to the inhibition that ion is transmitted
It is low, but covered effect has the trend of variation；It can be obtained by embodiment 4, embodiment 7 and embodiment 8, with porous graphene lamella hole
The increase of diameter, the cycle performance of material is deteriorated, and this is due to that bore dia is excessive, it is impossible to plays and fully coats nuclear structure surface
Effect.It can be obtained by each embodiment, the present invention has universality, be adapted to various lithium titanate anode materials and preparation method thereof.
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, the shell structure are uniformly wrapped on the nuclear structure
Surface, it is characterised in that the particle diameter of the nuclear structure is D1, and the thickness of the shell structure is h1,
Contain graphene in the shell structure, the graphene is porous graphene, the lamellar spacing h2 of the graphene≤
100nm；
Pore size distribution$ on the lamella of the porous graphene is in the slice plane of the graphene；The pore structure it is straight
Footpath is that the width of continuous part between D2, holes is d1, d1≤π * D1.
2. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the nuclear structure be primary particle structure,
Lithium titanate component is included in second particle structure or multiple particle structure, the nuclear structure.
3. the lithium titanate anode material described in a kind of claim 1, it is characterised in that connect between the holes of the porous graphene
The width of continuous part is the π D1/3 of d1≤2.
4. the lithium titanate anode material described in a kind of claim 1, it is characterised in that also include clad in the shell structure
Or/and the polymer carbonization component that monomer in situ polymerization is obtained.
5. the lithium titanate anode material described in a kind of claim 4, it is characterised in that the clad is traditional clad raw material
Charing is obtained；Traditional clad raw material be phenolic resin, melamine resin, Vinylidene Chloride, pitch, polyethylene, stearic acid,
It is PVC, polyacrylonitrile, natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers, polyethylene, polypropylene, polyamide, poly- to benzene
In naphthalate, nano cupric oxide, nano magnesia, nano-titanium oxide, nano aluminium oxide, nano-graphite, graphite flake
At least one；The monomer includes esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, poly-
Ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, divinylbenzene, trimethylol propane trimethyl acrylic acid
Ester, methyl methacrylate, N, N- DMAAs, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, propylene
Acid butyl ester, positive Hexyl 2-propenoate, 2- cyclohexyl acrylates, dodecyl acrylate, GDMA, polyethylene glycol
Dimethylacrylate, polyethylene glycol dimethacrylate, neopentylglycol diacrylate, 1,6-HD diacrylate
Ester, tetraethylene glycol diacrylate, tri (propylene glycol) diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation season
Penta tetrol acrylate, double-Glycerin tetraacrylate, pentaerythritol triacrylate, trimethylol propane trimethyl
Acrylate, glycerol propoxylate triacrylate, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane tris third
Olefin(e) acid ester, propoxylation trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylation
In trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate
It is at least one.
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, selection nuclear structural materials are standby；
Step 2, the clad slurry containing graphene sheet layer is prepared；
Step 3, the nuclear structural materials described in step 1 are placed in the slurry that step 2 is obtained and coated, is carbonized afterwards i.e.
Obtain 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 in the clad slurry
Also comprising traditional clad raw material or/and polymer monomer.
8. the preparation method of the lithium titanate anode material described in a kind of claim 7, it is characterised in that contain when in the clad
When having polymer monomer, after the step 3 cladding process, inducer need to be added and promote monomer in situ polymerization formation polymerization
Thing.
9. a kind of preparation method of the lithium titanate anode material described in claim 6, it is characterised in that the preparation described in step 2
Surfactant is additionally added during clad slurry containing graphene sheet layer, the surfactant includes wetting
At least one of agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent.
10. a kind of preparation method of the lithium titanate anode material described in claim 6, it is characterised in that the core knot described in step 1
Particle diameter D1≤100 μm of structure material；The width of continuous part is d1≤π * between the holes of porous graphene described in step 2
D1。
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| CN108741379A (en) * | 2018-06-25 | 2018-11-06 | 蚌埠科睿达机械设计有限公司 | A kind of sport footwear |
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