CN107316992A - Lithium titanate anode material and preparation method thereof - Google Patents
Lithium titanate anode material and preparation method thereof Download PDFInfo
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- 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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Abstract
The invention belongs to energy storage material technical 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 nano lithium titanate primary particle being filled in the porous leading electric network pore structure；Between the leading electric network and the nano lithium titanate primary particle, guidance electric network is distributed with, the leading electric network is closely joined together by the guidance electric network with the nano lithium titanate primary particle, 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 agent) of difficulty is dispersed, while ensuring to be close-coupled at one between the two
Rise, 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 nano lithium titanate primary particle in the porous leading electric network pore structure；The leading electric network and the nanometer
Between lithium titanate primary particle, guidance electric network is distributed with, the guidance electric network is by the leading electric network and the nanometer
Lithium titanate primary particle is closely joined together.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 nano lithium titanate one being filled in the pore structure of the leading electric network
Secondary particle；Guidance electric network, the guidance electricity are distributed between the leading electric network and the nano lithium titanate primary particle
The leading electric network is closely joined together by network with the nano lithium titanate primary particle.Shell structure refers to negative material
The materials such as general clad, predominantly pitch cladding, carbonization are obtained, therefore the present invention is not set forth in detail.
Improved as one kind of lithium titanate anode material of the present invention, the leading electric network is porous agraphitic carbon network knot
In structure, porous hard carbon network structure, opening graphene-structured, opening intumesced graphite structure, quasiflake graphite alkene structure at least
It is a kind of；The guidance electric network is obtained by high polymer material carbonization, the guidance electric network quality be the lithium titanate once
The 0.5%~10% of grain quality.
Improved as one kind of lithium titanate anode material of the present invention, the high polymer material is by high polymer monomer in-situ polymerization
And obtain.
Improved as one kind of lithium titanate anode material of the present invention, in the guidance electric network, in addition to it is conductive black, super
At least one of level conductive carbon, Ketjen black, CNT, graphene, acetylene black；The primary particle also includes non-nano titanium
Sour cathode of lithium 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 based anode material, tin base cathode material, transition metal nitride, tinbase are closed
At least one of gold, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy.
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：Mediated after primary particle, polymer monomer are mixed, obtain polymer monomer uniform
It is scattered in nanometer presoma on primary particle surface；
Step 2, electric network structure is dominated to prepare：Prepare the leading electric network structure with loose structure stand-by；
Step 3, fill：Presoma made from step 1 is filled into leading electric network structure；
Step 4, polymerisation：By the product of step 3, in the environment for being placed in initiator presence, promote to be scattered in once
The high polymer monomer polymerization on grain surface, obtains high molecular polymer；The polymer now generated will be primary particle and leading electricity
Network closely bonds together；
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, 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 material particle, tin base cathode material, transition metal nitride, kamash alloy, germanium-base alloy, aluminium base are closed
At least one of gold, antimony-containing alloy, magnesium base alloy；It can also add high molecular polymer, carbon source component when mediating reaction, lead
Electric agent 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, kneading process described in step 1 is：By nanometer
Primary particle, surfactant 1, polymer monomer, solvent 1 are mediated, and obtain mixture 1；By conductive agent component, surfactant
2nd, solvent 2 is mediated, and obtains mixture 2；Mixture 1 is blended with mixture 2 again, the blending method includes kneading, ball milling, sand
At least one of mill, high-pressure homogeneous, high speed shear, are uniformly dispersed and obtain precursor pulp.
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 porous agraphitic carbon network structure and porous hard carbon network structure：Carbon source component and carbon after foaming agent reaction
The directly reaction of change, template, polymer obtains being carbonized after loose structure；
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-
Spar ink (can prepare quasiflake graphite alkene, change and be closely joined together between graphene sheet layer, while between lamella point
There is the gap structure of prosperity in portion, is easy to the filling of primary particle；Micro crystal graphite alkene particle size is smaller simultaneously, and what is prepared is compacted
Worm shape graphene particle diameter is 10 μm or so, is matched very much with final finished lithium titanate anode particle diameter) it is raw material, control oxidation
(main oxygenerating degree is moderate, and degree of oxidation is too low, it is impossible to form loose structure for intercalation degree；Degree of oxidation is too high, reduction
During graphite flake layer will be completely exfoliated and come, it is impossible to form the loose structure linked together), reduce afterwards, you can obtain
The loose structure that lamella links together, is open between lamella and lamella between same coccolith ink.
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, the surfactant 1 accounts for nano barium titanate
The 0.01-10% of lithium quality, slurry solid content is not less than 1%；The surfactant 2 accounts for the 0.01-10% of conductive agent quality,
Slurry solid content is not less than 0.5%.
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, which is surfactant 2, includes wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, latent molten
At least one of agent；The solvent 2 is water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethyl
At least one of acid amides, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.
Improved as one kind of lithium titanate anode material preparation method of the present invention, initiator can also be added in step 1, but
Now pay particular attention to control condition so that before filling step described in step 3 is completed, initiator will not trigger monomer to send out
Raw polymerisation；Reaction condition is controlled again after the completion of process to be filled, is promoted monomer to occur polymerization and is formed polymer.
The advantage of the invention is that：
1. the leading electric network structure of the present invention can play dual parts of electronics conduction and fixed primary particle structure,
While ensuring excellent conductive capability inside lithium titanate anode material particle, the macrostructure of stabilized lithium titanate material particle；
2. teach electric network structure to be closely connected leading electric network structure with primary particle, the contact of increase between the two
Area, reduces contact resistance, it is ensured that all primary particles effectively can be connected with leading electric network close structure, forms electronics
Path；So that it is guaranteed that the chemical property of each primary particle can fully play out in cyclic process, while maximum
The resistance of the reduction material internal of limit；
3. in preparation process, using the low high polymer monomer of viscosity and primary particle mediate and disperse, it can be ensured that receive
Rice primary particle is dispersed, and high polymer monomer is uniformly distributed in a nanometer primary particle surface；
4. the presoma with more low viscosity (because high polymer monomer viscosity is low), it is easier to be filled into leading electric network
Pore structure in, it is ensured that fill up primary particle in the hole of leading electric network loose structure.
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=100:2:1), (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, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 15%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Step 3, fill：The quasiflake graphite alkene that step 2 is obtained is vacuumized, and is placed in afterwards in the presoma of step 1, then
Apply pressure into presoma, while ultrasonic vibration so that presoma is inserted in quasiflake graphite alkene pore structure, isolated to fill out
Quasiflake graphite alkene full of 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 quasiflake graphite alkene 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 quasiflake graphite alkene lamella.
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.
Embodiment 2, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 5%, it
After to be thermally treated resulting in quasiflake graphite alkene 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, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 20%, it
After to be thermally treated resulting in quasiflake graphite alkene 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, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 25%, it
After to be thermally treated resulting in quasiflake graphite alkene 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, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 40%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 6, is that the present embodiment comprises the following steps with comparative example difference：
Step 1, prepared by presoma：By lithium titanate, the N that particle diameter is 100nm, N- DMAAs, different monooctyl ester sulfonic acid
(mass ratio is lithium titanate to sodium:N, N- DMAA：Different dioctyl sodium sulfosuccinate=100:0.5:After 1), ethanol is mixed (Gu
Content is 10%) to mediate, and revolves round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma, then
The special butyl ester of perbenzoic acid is added to stir；
Step 2, opening 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 the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 20%, it
After be thermally treated resulting in opening expanded graphite it is stand-by；
Step 3, fill：The opening expanded graphite that step 2 is obtained is vacuumized, and is placed in afterwards in the presoma of step 1, then
Apply pressure into presoma, while ultrasonic vibration so that presoma is inserted in opening Porous Structure of Expanded Graphite, isolated to fill out
Opening expanded graphite full of presoma；
Step 4, polymerisation：Heating, promotes to be scattered in the methyl methacrylate polymerization on primary particle surface, so that will
Together with primary particle is closely bonded with opening expanded graphite lamella.
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.
Embodiment 7, difference from Example 6 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：By lithium titanate, the N that particle diameter is 100nm, N- DMAAs, different monooctyl ester sulfonic acid
(mass ratio is lithium titanate to sodium:N, N- DMAA：Different dioctyl sodium sulfosuccinate=100:1:After 1), ethanol is mixed (admittedly contain
Measure 10%) to mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma, then add
Enter the special butyl ester of perbenzoic acid to stir；
Remaining is same as Example 6, repeats no more.
Embodiment 8, difference from Example 6 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：By lithium titanate, the N that particle diameter is 100nm, N- DMAAs, different monooctyl ester sulfonic acid
(mass ratio is lithium titanate to sodium:N, N- DMAA：Different dioctyl sodium sulfosuccinate=100:2:After 1), ethanol is mixed (admittedly contain
Measure 10%) to mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma, then add
Enter the special butyl ester of perbenzoic acid to stir；
Remaining is same as Example 6, repeats no more.
Embodiment 9, difference from Example 6 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：By lithium titanate, the N that particle diameter is 100nm, N- DMAAs, different monooctyl ester sulfonic acid
(mass ratio is lithium titanate to sodium:N, N- DMAA：Different dioctyl sodium sulfosuccinate=100:5:After 1), ethanol is mixed (admittedly contain
Measure 10%) to mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma, then add
Enter the special butyl ester of perbenzoic acid to stir；
Remaining is same as Example 6, repeats no more.
Embodiment 10, difference from Example 6 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：By lithium titanate, the N that particle diameter is 100nm, N- DMAAs, different monooctyl ester sulfonic acid
(mass ratio is lithium titanate to sodium:N, N- DMAA：Different dioctyl sodium sulfosuccinate=100:10:After 1), ethanol is mixed (Gu
Content is 10%) to mediate, and revolves round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma, then
The special butyl ester of perbenzoic acid is added to stir；
Remaining is same as Example 6, repeats no more.
Embodiment 11, difference from Example 1 is, the present embodiment comprises the following steps：
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=100:2:1), (solid content is after NMP mixing
2%) mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma；
Remaining is same as Example 1, repeats no more.
Embodiment 12, difference from Example 1 is, the present embodiment comprises the following steps：
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=100:2:1), (solid content is after NMP mixing
20%) mediate, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain dispersed presoma；
Remaining is same as Example 1, repeats no more.
Embodiment 13, 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+Delanium) for GDMA, hexadecyldimethyl benzyl ammonium allyl ammonium chloride:
GDMA:Hexadecyldimethyl benzyl ammonium allyl ammonium chloride=100:2:1), (solid content is after water mixing
10%) mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By graphene, polyoxyethylene alkane
Base phenolic ether (graphene:Polyoxyethylated alkyl phenol=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 is (lithium titanate+people
Make graphite):Graphene=100:4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate
Obtained after 6h polymer monomer be uniformly wrapped on that primary particle surface, polymer monomer and graphene uniform be scattered, graphene with
The dispersed presoma of primary particle；
Step 2, agraphitic carbon is dominated electric network structure and prepared：Selection pitch is mixed with foaming agent, carries out foaming instead afterwards
It should again be carbonized, obtain agraphitic carbon and dominate electric network structure.
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 13 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 carbon material are prepared by following flow in 25 DEG C of environment
Battery core carry out loop test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand 3min；1C is permanent
Stream is discharged to 1.5V, obtains discharge capacity D1；Stand 3min, " 1C constant-current charges to 2.8V, 2.8V constant-voltage charges to 0.1C；It is quiet
Put 3min；1C constant-current discharges obtain discharge capacity Di to 1.5V；Stand 3min " to repeat to obtain D1000 999 times, complete to follow afterwards
Ring 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 chemical property of the battery core of lithium titanate anode material system assembling prepared by table 1, different comparative examples and embodiment
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 5 can be obtained, with the increase of oxygen-containing functional group, and the battery performance that lithium titanate electrode material is assembled first improves and had afterwards
The trend of variation, this be due to oxygen-containing functional group very little, the stephanoporate framework space prepared is few, the primary particle amount of filling compared with
It is few；Oxygen-containing functional group is excessive, and the stephanoporate framework space of preparation is too many, it is impossible to give full play to the electric conductivity of skeleton.Contrast is implemented
Example 6-, which implements row 10, to be obtained, and with the increase for teaching electric network quality, battery performance first improves to be deteriorated afterwards, because teaching electricity
Network content is too low, it is impossible to give full play to its electric conductivity；Inside too high levels, the lithium titanate material second particle prepared
Metatitanic acid lithium content is low, porosity is big, and the capacity of material is low, be easier aerogenesis.Comparative example 1,11,12 can be obtained, primary particle
During kneading, it is also desirable to control solid content, because solid content is too high, disperse uneven, solid content is too low, production cost is high, and meeting
Influence filling effect.It can be obtained by each embodiment, the present invention has universality.
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
Lithium titanate primary particle；Guidance electric network, institute are distributed between the leading electric network and the nano lithium titanate primary particle
Guidance electric network is stated to be closely joined together the leading electric network with the nano lithium titanate primary particle.
2. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the leading electric network is porous unformed
Carbon network structure, porous hard carbon network structure, opening graphene-structured, opening intumesced graphite structure, quasiflake graphite alkene structure
At least one of；The guidance electric network is obtained by high polymer material carbonization, and the guidance electric network quality is the metatitanic acid
The 0.5%~10% of lithium primary particle quality.
3. the lithium titanate anode material described in a kind of claim 2, it is characterised in that the high polymer material is by high polymer monomer
In-situ polymerization and obtain.
4. the lithium titanate anode material described in a kind of claim 1, it is characterised in that 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；The primary particle is also wrapped
Include non-nano lithium titanate anode particle；The non-nano lithium titanate anode particle is that native graphite, Delanium, mesocarbon are micro-
Ball, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, silicon based anode material, tin base cathode material, transitional metal nitride
At least one of thing, kamash alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy.
5. 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：Mediated after primary particle, polymer monomer are mixed, obtain polymer monomer and uniformly disperse
Presoma in nanometer primary particle surface；
Step 2, electric network structure is dominated to prepare：Prepare the leading electric network structure with loose structure stand-by；
Step 3, fill：Presoma made from step 1 is filled into leading electric network structure；
Step 4, polymerisation：By the product of step 3, in the environment for being placed in initiator presence, promote to be scattered in primary particle table
The high polymer monomer polymerization in face, obtains high molecular polymer；
Step 5, the product of step 4 is coated, being carbonized obtains finished product lithium titanate anode material.
6. a kind of preparation method of the lithium titanate anode material described in claim 5, it is characterised in that polymer described in step 1
Monomer includes esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol dimethyl allene
Acid esters, polyethyleneglycol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl methacrylate,
N, N- DMAA, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate, positive acrylic acid oneself
It is ester, 2- cyclohexyl acrylates, dodecyl acrylate, GDMA, polyethylene glycol dimethacrylate, poly-
Ethylene glycol dimethacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, tetraethylene glycol diacrylate
Ester, tri (propylene glycol) diacrylate, ethoxyquin tetramethylol methane tetraacrylate, third oxidation pentaerythritol acrylate, it is double-
Glycerin tetraacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate, glycerol propoxylate
Triacrylate, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylates, the hydroxyl of propoxylation three
Propane tri, ethoxylated trimethylolpropane triacrylate, the propylene of ethoxylated trimethylolpropane three
At least one of acid esters, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate；Described in step 4
Initiator includes isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, peroxidating
The special butyl ester of dibenzoyl, dilauroyl peroxide, perbenzoic acid, peroxide tert pivalate ester, dicetyl peroxydicarbonate two are different
At least one of propyl ester, di-cyclohexylperoxy di-carbonate.
7. a kind of preparation method of the lithium titanate anode material described in claim 5, 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 are additionally added when closing reaction.
8. the preparation method of the lithium titanate anode material described in a kind of claim 5, it is characterised in that 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.
9. the preparation method of the lithium titanate anode material described in a kind of claim 5, it is characterised in that electricity is dominated described in step 2
Network be porous agraphitic carbon network structure, porous hard carbon network structure, opening graphene-structured, opening intumesced graphite structure,
At least one of quasiflake graphite alkene structure, wherein, the system of porous agraphitic carbon network structure and porous hard carbon network structure
Preparation Method includes：Carbon source component obtains porous structure polymer with carbonization, template, polymer directly reaction after foaming agent reaction
After be carbonized；Opening graphene-structured, opening intumesced graphite structure and the preparation method of quasiflake graphite alkene structure are：With scale stone
Black or micro crystal graphite is raw material, and control oxidation intercalation degree is reduced afterwards, you can obtain same coccolith black interior lamella and lamella
At least a portion links together, while forming the loose structure of opening between lamella and lamella again.
10. a kind of preparation method of the lithium titanate anode material described in claim 5, it is characterised in that the filling described in step 3
Process is：
Leading electric network structural material is pre-processed, the pretreatment includes surface active or/and addition surfactant；
Before filling, leading electric network structural material is placed in vacuum environment and vacuumized, the air in discharge pore structure, before being
The filling vacating space of body is driven, 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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