CN107808954A - A kind of lithium titanate cladding hard carbon composite and preparation method thereof - Google Patents
A kind of lithium titanate cladding hard carbon composite and preparation method thereof Download PDFInfo
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- CN107808954A CN107808954A CN201710976055.XA CN201710976055A CN107808954A CN 107808954 A CN107808954 A CN 107808954A CN 201710976055 A CN201710976055 A CN 201710976055A CN 107808954 A CN107808954 A CN 107808954A
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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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- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium titanate to coat hard carbon composite, and it includes hard carbon, is coated on the metatitanic acid lithium layer on hard carbon surface, and is coated on the carbon-coating on lithium titanate surface；Its preparation method is using compound containing Ti as raw material, add peroxide and weak base, stirring, then hard carbon is introduced in hydrolytic process is stirred, add size of the mixed solution of appropriate amount of deionized water and alcohol for regulating and controlling nanosphere, hydrolyze mixture simultaneously, lithium source is introduced after this step, then adding structure directing agent makes lithium titanate precursor glomeration, obtain lithium titanate/hard carbon presoma, lithium titanate/hard carbon presoma is put into baking oven and dried, then sintering of being annealed in the high temperature furnace full of inert gas is placed into, lithium titanate cladding hard carbon composite is made.The rapid charging performance of the high power capacity of hard carbon and lithium titanate is effectively combined, fabricated in situ, settled at one go in one layer of lithium titanate of hard carbon Surface coating by the present invention, convenient and swift.
Description
Technical field
The invention belongs to the technical field of lithium ion battery electrode material, more particularly to a kind of lithium titanate cladding hard carbon are compound
Material and preparation method thereof.
Background technology
Current city environmental pollution getting worse, urban transportation discharge especially public transport bus exhaust emissions turn into important
Pollution sources.The development of pure electric bus plays an important roll to alleviating urban air pollution especially haze.Electric automobile is for I
The important force of state's development New Energy Industry, and the emerging strategic industries that countries in the world are competitively fought for.New-energy automobile is outstanding
It has become the strategic industry given priority in Shenzhen.Accelerate to cultivate and develop new-energy automobile industry, be that Shenzhen should
To the energy and environment challenge, the important selection for promoting the upgrading of orthodox car industrial transformation.Because electric bus need to carry largely
Battery, manufacturing cost is high, and therefore, electric bus gradually develops to short distance quickly-chargeable and long-life direction.Extensively should at present
Lithium ion battery is using graphite as negative material, and in its quick or low temperature charging process, lithium metal is easily analysed in graphite surface
Go out, have a strong impact on the security performance and cycle life of battery, negative electrode of lithium ion battery seriously constrains low cost pure electric bus
Development.Therefore, development can quickly and low temperature charge, the lithium ion battery negative material of long circulation life and high safety performance
With important value.
Spinel structural lithium titanate material theoretical capacity is 175mAhg-1, in charge and discharge process Volume Changes it is very small,
Stability Analysis of Structures, there is three-dimensional lithium ion diffusion admittance, because its intercalation potential platform is higher (1.55V vs Li+/Li), lithium
Ion is bigger than graphite in the diffusion coefficient of lithium titanate intracell, so charged under quick and low temperature, lithium ion is not yet
It can deposit, make it have very excellent cyclic reversibility, security, low temperature and rapid charging performance, be to prepare high power length
Life-span and can fast charge lithium ion battery important negative material.However, the intrinsic ion of lithium titanate material, electronic conductivity and ratio
Capacity is relatively low, is only 70~80Wh/kg by the lithium-ion-power cell energy density that negative pole assembles of lithium titanate, and fast charge is electronic
The comparatively ideal electrokinetic cell energy density of bus need to reach 120Wh/kg.Lithium titanate anode material is typically by nanoscale primary particle
Manufactured micrometer level porous spherical second particle, its porosity characteristic reduce the bulk density of lithium titanate, and particle is frangible.
Hard carbon cathode material has higher specific capacity and good fast charging and discharging performance, and specific capacity is generally greater than stone
Ink, as phenolic resin is pyrolyzed carbon ratio 400~500mAh/g of capacity, poly furfuryl alcohol pyrolytic carbon specific capacity about 400mAh/g, partial thermal decomposition
Carbon is even as high as 900mAh/g, and has higher charge and discharge potential.The density of hard carbon cathode material is smaller, specific surface area compared with
Greatly, first charge-discharge efficiency is relatively low, and security is poor.
The content of the invention
Present invention seek to address that the dissatisfactory technical problem of lithium cell cathode material in the prior art, there is provided a kind of metatitanic acid
Lithium coats hard carbon composite and its in-situ preparation method.The lithium titanate prepared using this method coats hard carbon composite, tool
Have the advantages that high power capacity can fast charge.
In order to achieve the above object, present invention employs following technical scheme：
A kind of lithium titanate coats hard carbon composite, including hard carbon, is coated on the metatitanic acid lithium layer on hard carbon surface, and cladding
Carbon-coating on lithium titanate surface.
As the improved technical scheme of the present invention, the metatitanic acid lithium layer is made up of lithium titanate nanosphere.
Preferably, particle diameter≤200nm of the lithium titanate nanosphere, particle diameter≤10 μm of the hard carbon.
Preferably, the hard carbon quality is the 29%~45% of lithium titanate quality.
The present invention also provides a kind of preparation method of lithium titanate cladding hard carbon composite, comprises the following steps：S1：With containing
Ti compounds are raw material, add peroxide and weak base；S2：S1 mixture is stirred while adding hard carbon；S3：By go from
Sub- water is 1 with alcohol by volume ratio:0.5~5 blendes together mixed solution in advance, then adds in S2 mixture, makes the water of compound containing Ti
Solution is complete；S4:Lithium source is introduced in S3 hydrolysate, reaction obtains lithium titanate nanosphere, wherein, the compound containing Ti and lithium
The ratio between the amount of material in source is 1:1~2；S5：Structure directing agent is added in S4 reactant, obtains lithium titanate/hard carbon forerunner
Body；S6：Lithium titanate/hard carbon presoma is put into baking oven and dried, then place into 600~900 DEG C full of inert gas
1~10h of annealing sintering in high temperature furnace, lithium titanate cladding hard carbon composite is made.
Preferably, the compound containing Ti is mainly titanium nitride, titanium carbide, titanium trichloride, titanium chloride, butyl titanate
In one of which.
Further, the peroxide is 25~35% hydrogen peroxide, and the weak base is 20~35% ammoniacal liquor, its
In, every gram of compound containing Ti needs 50~80mL of hydrogen peroxide, and every gram of compound containing Ti needs 20~30mL of ammoniacal liquor.
Preferably, the hard carbon is included in phenolic resin pyrolysis carbon, glycan alcohol pyrolytic carbon, glucose pyrolytic carbon, carbon black
It is at least one.
Preferably, the hard carbon specific capacity is more than or equal to 200mAh/g, hard carbon particle diameter≤10 μm.
Preferably, the hard carbon quality is the 29%~45% of lithium titanate theoretical yield.
Further, every gram of compound containing Ti needs 200~800mL of mixed solution of deionized water and alcohol in S3.
Preferably, the lithium source be lithium hydroxide, lithium acetate, lithium carbonate, carbonic acid dihydro lithium, in lithium dihydrogen phosphate at least
One kind, and the reaction environment in S4 is alkalescent.
Preferably, the structure directing agent is polyvinylpyrrolidone, cetyl trimethylammonium bromide, cetyl
Amine, polyoxyethylene fatty acid ester class surfactant, polyoxyethylene aliphatic alcohol ether class surfactant, polyoxyethylene-polyoxy third
At least one of alkene copolymer class surfactant.Preferably, the usage amount of the structure directing agent is the compound containing Ti
20%~60%.
Beneficial effect
The present invention is in one layer of lithium titanate of hard carbon Surface coating, effectively by the high power capacity of hard carbon and the rapid charging performance of lithium titanate
It is combined, fabricated in situ, settles at one go, it is convenient and swift.In addition, lithium titanate top layer is also covered with one layer of carbon coating, it is effectively kept away
Exempt from the aerogenesis problem of lithium titanate and electrolyte contacts, can further improve the electrification of lithium titanate cladding hard carbon cathode composite
Learn performance.
Brief description of the drawings
The preparation method flow chart of Fig. 1 present invention；
Fig. 2 is the XRD that lithium titanate made from embodiment 1 coats hard carbon composite；
Fig. 3 is the SEM figures that lithium titanate made from embodiment 1 coats hard carbon composite；
Fig. 4 is the SEM enlarged drawings that lithium titanate made from embodiment 1 coats hard carbon composite；
Fig. 5 is that lithium titanate made from embodiment 1 coats cyclic curve of the hard carbon composite under 1C multiplying powers；
Fig. 6 is that lithium titanate made from embodiment 1 coats cyclic curve of the hard carbon composite under 10C multiplying powers；
Fig. 7 is the SEM enlarged drawings of lithium titanate/hard carbon composite made from embodiment 5.
Embodiment
In order that those skilled in the art becomes apparent from legibly understanding the present invention, in conjunction with embodiment and attached
Figure, the present invention is described in detail.
Embodiment 1
Lithium titanate disclosed by the invention coats hard carbon composite, including hard carbon, the metatitanic acid lithium layer for being coated on hard carbon surface
And it is coated on the carbon-coating on lithium titanate surface.Wherein, the metatitanic acid lithium layer is made up of lithium titanate nanosphere.Preferably, the titanium
Particle diameter≤200nm of sour lithium nanosphere, particle diameter≤10 μm of the hard carbon.Preferably, the hard carbon quality is lithium titanate quality
29%~45%.
The preparation method of above-mentioned lithium titanate cladding hard carbon composite as shown in figure 1, including：
S1：Using compound containing Ti as raw material, peroxide and weak base are added；
S2：S1 mixture is stirred while adding hard carbon；
S3：It is 1 by deionized water and alcohol by volume ratio:0.5~5 blendes together mixed solution in advance, then adds S2 mixture
In, make compound hydrolysis containing Ti complete；
S4:Introduce lithium source in S3 hydrolysate, reaction obtains lithium titanate nanosphere, wherein, the compound containing Ti and
The ratio between amount of material of lithium source is 1:1~2；
S5：Structure directing agent is added in S4 reactant, obtains lithium titanate/hard carbon presoma；
S6：Lithium titanate/hard carbon presoma is put into baking oven and dried, 600~900 DEG C is then placed into and is full of indifferent gas
1~10h of annealing sintering in the high temperature furnace of body, lithium titanate cladding hard carbon composite is made.
Wherein, the usage amount of each raw material and technological parameter are as follows in S1-S6：0.25gTiN, 28mL deionized water, 16mL
30% hydrogen peroxide, 6mL 28% ammoniacal liquor, 150mg hard carbons (glucose hydro-thermal and obtain), stir 30 minutes；Add 50mL go from
Sub- water and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, add 100mgPVP, stirring is dried after 30 minutes at 80 DEG C
It is dry；The high temperature anneal 5h at 800 DEG C, lithium titanate cladding hard carbon composite is made.
Experimental result：Fig. 3 and Fig. 4 be lithium titanate coat hard carbon composite SEM figure, as seen from the figure, hard carbon surface by
Lithium titanate bead completely coats, and the average grain diameter of lithium titanate bead is about 100nm.Fig. 5 and Fig. 6 is that lithium titanate cladding hard carbon is compound
Material is as cathode of lithium battery, the cycle charge-discharge curve under 1C and 10C multiplying powers.Lithium titanate produced by the present invention is coated into hard carbon
Composite and documents 1 (a kind of method for preparing carbon coating lithium titanate, publication number CN104600280A, publication date
2015.05.06 the cycle charge discharge electrical property of the composite of carbon coating lithium titanate made from) is contrasted, as shown in table 1.By
Table 1 is visible, and lithium titanate cladding hard carbon composite produced by the present invention has more preferable charge-discharge performance.
The present invention of table 1 and metatitanic acid lithium/carbon composite material cycle charge-discharge performance comparison made from documents 1
Embodiment 2
Preparation method such as embodiment 1 in embodiment 2, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 200mg hard carbons (glucose hydro-thermal and obtain), stirring 30
Minute；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, add 100mgPVP, stirring 30
In 80 DEG C of drying after minute；The high temperature anneal 5h at 800 DEG C.
Experimental result：Hard carbon surface is coated by lithium titanate bead, and cladding is complete.
Embodiment 3
Preparation method such as embodiment 1 in embodiment 3, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 250mg hard carbons (glucose hydro-thermal and obtain), stirring 30
Minute；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, add 100mgPVP, stirring 30
In 80 DEG C of drying after minute；The high temperature anneal 5h at 800 DEG C.
Experimental result：Hard carbon surface is coated by lithium titanate bead, and cladding is complete.
Embodiment 4
Preparation method such as embodiment 1 in embodiment 4, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, 16mL hydrogen peroxide, 6mL ammoniacal liquor, 300mg hard carbons (glucose hydro-thermal and obtain), stir 30 minutes；Add 50mL
Deionized water and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, add 100mgPVP, 80 after stirring 30 minutes
DEG C drying；The high temperature anneal 5h at 800 DEG C.
Experimental result：Cladding is loose, and lithium titanate bead has only coated part hard carbon.
Embodiment 5
Preparation method such as embodiment 1 in embodiment 5, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 150mg hard carbons (glucose hydro-thermal and obtain), stirring 30
Minute；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, at 80 DEG C after stirring 30 minutes
Drying；The high temperature anneal 5h at 800 DEG C.
Experimental result：Lithium titanate fails balling-up, is directly in granular form epitaxial growth on hard carbon surface.
Embodiment 6
Preparation method such as embodiment 1 in embodiment 6, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 200mg hard carbons (glucose hydro-thermal and obtain), stirring 30
Minute；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, at 80 DEG C after stirring 30 minutes
Drying；The high temperature anneal 5h at 800 DEG C.
Experimental result：Lithium titanate fails balling-up, is directly in granular form epitaxial growth on hard carbon surface.
Embodiment 7
Preparation method such as embodiment 1 in embodiment 7, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 300mg hard carbons (glucose hydro-thermal and obtain), stirring 30
Minute；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.14g lithium hydroxides are added, at 80 DEG C after stirring 30 minutes
Drying；The high temperature anneal 5h at 800 DEG C.
Experimental result：Lithium titanate fails balling-up, is directly in granular form epitaxial growth on hard carbon surface.
Embodiment 8
Preparation method such as embodiment 1 in embodiment 8, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 35%, the ammoniacal liquor of 6mL 35%, 200mg hard carbons (are obtained) by glucose hydro-thermal, stirring
30 minutes；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.17g lithium hydroxides are added, 80 after stirring 30 minutes
DEG C drying；The high temperature anneal 1h at 900 DEG C.
Experimental result：Cladding is loose, lithium titanate bead only covered section hard carbon.
Embodiment 9
Preparation method such as embodiment 1 in embodiment 9, the usage amount and technological parameter of its each raw material are as follows：0.25gTiN,
28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 200mg hard carbons (are obtained) by glucose hydro-thermal, stirring
30 minutes；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.17g lithium hydroxides are added, 80 after stirring 30 minutes
DEG C drying；The high temperature anneal 10h at 900 DEG C.
Experimental result：Cladding is loose, and lithium titanate crystallization is long, only covered section hard carbon.Research finds that sintering temperature is to titanium
Sour lithium cladding influence is very big, and temperature is too low, and the time is too short, can not crystallize to form lithium titanate；Many dephasigns are had, temperature is too high,
Overlong time, then crystallization can be destroyed, excessive grain is grown up.
Embodiment 10
Preparation method such as embodiment 1 in embodiment 10, the usage amount and technological parameter of its each raw material are as follows：
0.25gTiN, 28mL deionized water, the hydrogen peroxide of 16mL 30%, 6mL28% ammoniacal liquor, 200mg hard carbons are (by glucose hydro-thermal
), stir 30 minutes；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.17g lithium hydroxides are added, stir 30 points
In 80 DEG C of drying after clock；The high temperature anneal 1h at 600 DEG C.
Experimental result：Cladding is loose, lithium titanate bead only covered section hard carbon.
Embodiment 11
Preparation method such as embodiment 1 in embodiment 11, the usage amount and technological parameter of its each raw material are as follows：
0.25gTiN, 28mL deionized water, the hydrogen peroxide of 16mL 30%, 6mL28% ammoniacal liquor, 200mg hard carbons are (by glucose hydro-thermal
), stir 30 minutes；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.17g lithium hydroxides are added, stir 30 points
In 80 DEG C of drying after clock；The high temperature anneal 10h at 600 DEG C.
Experimental result：Hard carbon surface is coated by lithium titanate bead, and cladding is complete.
Embodiment 12
Preparation method such as embodiment 1 in embodiment 12, the usage amount and technological parameter of its each raw material are as follows：
0.25gTiN, 28mL deionized water, 40mL25% hydrogen peroxide, 7.5mL25% ammoniacal liquor, 200mg hard carbons are (by glucose hydro-thermal
), stir 30 minutes；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.17g lithium hydroxides are added, stir 30 points
In 80 DEG C of drying after clock；The high temperature anneal 5h at 800 DEG C.
Experimental result：Cladding is loose, and lithium titanate bead coats most of hard carbon.
Embodiment 13
Preparation method such as embodiment 1 in embodiment 13, the usage amount and technological parameter of its each raw material are as follows：
0.25gTiN, 28mL deionized water, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 200mg hard carbons are (by glucose hydro-thermal
), stir 30 minutes；Add 30mL deionized waters and 150mL alcohol, lasting stirring；0.14g lithium hydroxides are added, stir 30 points
In 80 DEG C of drying after clock；The high temperature anneal 5h at 800 DEG C.
Experimental result：Cladding is loose, and lithium titanate bead coats most of hard carbon, and the particle diameter of lithium titanate is less than or equal to
60nm。
Embodiment 14
Preparation method such as embodiment 1 in embodiment 14, the usage amount and technological parameter of its each raw material are as follows：
0.25gTiN, 28mL deionized water, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 200mg hard carbons are (by glucose hydro-thermal
), stir 30 minutes；Add 30mL deionized waters and 150mL alcohol, lasting stirring；0.09g lithium hydroxides are added, stir 30 points
In 80 DEG C of drying after clock；The high temperature anneal 5h at 800 DEG C.
Experimental result：Cladding is loose, and lithium titanate bead coats most of hard carbon, and the particle diameter of lithium titanate is less than or equal to
60nm.Research finds that the more balls of alcohol are smaller, when deionized water and the ratio of alcohol exceed 1:During 0.5~5 scope, metatitanic acid
Lithium can not balling-up.
Embodiment 15
Preparation method such as embodiment 1 in embodiment 15, the usage amount and technological parameter of its each raw material are as follows：
0.25gTiN, 28mL deionized water, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, 200mg hard carbons (carbon black), stir 30 points
Clock；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.32g lithium acetates are added, add 150mgCTAB, stir 30 points
In 80 DEG C of drying after clock；The high temperature anneal 5h at 800 DEG C.
Experimental result：Cladding is loose, obtains the hard carbon of the big ball cladding of lithium titanate, and the particle diameter of lithium titanate is more than 120nm.
Embodiment 16
Preparation method such as embodiment 1 in embodiment 15, the usage amount and technological parameter of its each raw material are as follows：0.25g titaniums
Sour four butyl esters, 28mL deionized waters, the hydrogen peroxide of 16mL 30%, the ammoniacal liquor of 6mL 28%, (phenolic resin is pyrolyzed 200mg hard carbons
Carbon), stir 30 minutes；Add 50mL deionized waters and 100mL alcohol, lasting stirring；0.32g lithium dihydrogen phosphates are added, are added
50mg HAD, stirring are dried after 30 minutes at 80 DEG C；The high temperature anneal 5h at 800 DEG C.
Experimental result：Cladding is loose, obtains the hard carbon of lithium titanate bead cladding, and the particle diameter of lithium titanate is less than 100nm.
Obviously, above-described embodiment is used for the purpose of clearly demonstrating example, rather than the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.As long as made on the basis of the embodiment of the present invention
The change scheme of common-sense, among protection scope of the present invention.
Claims (10)
1. a kind of lithium titanate coats hard carbon composite, it is characterised in that：Including hard carbon, the lithium titanate on hard carbon surface is coated on
Layer, and it is coated on the carbon-coating on lithium titanate surface.
2. lithium titanate according to claim 1 coats hard carbon composite, it is characterised in that：The metatitanic acid lithium layer is by metatitanic acid
Lithium nanosphere forms;Preferably, particle diameter≤200nm of the lithium titanate nanosphere, particle diameter≤10 μm of the hard carbon.
3. lithium titanate according to claim 1 coats hard carbon composite, it is characterised in that：The hard carbon quality is metatitanic acid
The 29%~45% of lithium quality.
4. a kind of preparation method of lithium titanate cladding hard carbon composite, comprises the following steps：
S1：Using compound containing Ti as raw material, peroxide and weak base are added；
S2：S1 mixture is stirred while adding hard carbon；
S3：It is 1 by deionized water and alcohol by volume ratio:0.5~5 blendes together mixed solution in advance, then adds in S2 mixture, makes
Compound hydrolysis containing Ti is complete；
S4:Lithium source is introduced in S3 hydrolysate, reaction obtains lithium titanate nanosphere, wherein, the compound containing Ti and lithium source
The ratio between the amount of material be 1:1~2；
S5：Structure directing agent is added in S4 reactant, obtains lithium titanate/hard carbon presoma；
S6：Lithium titanate/hard carbon presoma is put into baking oven and dried, then place into 600~900 DEG C full of inert gas
1~10h of annealing sintering in high temperature furnace, lithium titanate cladding hard carbon composite is made.
5. the preparation method of lithium titanate cladding hard carbon composite according to claim 4, it is characterised in that：It is described to contain Ti
Compound is mainly the one of which in titanium nitride, titanium carbide, titanium trichloride, titanium chloride, butyl titanate.
6. the preparation method of lithium titanate cladding hard carbon composite according to claim 4, it is characterised in that：The peroxide
Compound is 25~35% hydrogen peroxide, and the weak base is 20~35% ammoniacal liquor, wherein, every gram of compound containing Ti needs hydrogen peroxide
50~80mL, every gram of compound containing Ti need 20~30mL of ammoniacal liquor.
7. the preparation method of lithium titanate cladding hard carbon composite according to claim 4, it is characterised in that：The hard carbon
Including at least one of phenolic resin pyrolysis carbon, glycan alcohol pyrolytic carbon, glucose pyrolytic carbon, carbon black；Preferably, the hard carbon
Specific capacity is more than or equal to 200mAh/g, hard carbon particle diameter≤10 μm；Preferably, the hard carbon quality is lithium titanate theoretical yield
29%~45%.
8. the preparation method of lithium titanate cladding hard carbon composite according to claim 4, it is characterised in that：Every gram contains Ti
Compound needs 200~800mL of mixed solution of deionized water and alcohol.
9. the preparation method of lithium titanate cladding hard carbon composite according to claim 4, it is characterised in that：The lithium source
For at least one of lithium hydroxide, lithium acetate, lithium carbonate, carbonic acid dihydro lithium, lithium dihydrogen phosphate, and the reaction environment in S4 is
Alkalescent.
10. the preparation method of lithium titanate cladding hard carbon composite according to claim 4, it is characterised in that：The knot
Structure directed agents are polyvinylpyrrolidone, cetyl trimethylammonium bromide, hexadecylamine, polyoxyethylene fatty acid ester class table
In face activating agent, polyoxyethylene aliphatic alcohol ether class surfactant, Pluronic F68 class surfactant
It is at least one.
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| CN114094070A (en) * | 2021-11-10 | 2022-02-25 | 云南中晟新材料有限责任公司 | Titanium niobate-coated hard carbon composite material and preparation method thereof |
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| CN109473654A (en) * | 2018-11-22 | 2019-03-15 | 成都先进金属材料产业技术研究院有限公司 | Li4Ti5O12- TiN-TiC material and preparation method thereof |
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| CN114094070A (en) * | 2021-11-10 | 2022-02-25 | 云南中晟新材料有限责任公司 | Titanium niobate-coated hard carbon composite material and preparation method thereof |
| CN114094070B (en) * | 2021-11-10 | 2024-03-29 | 云南中晟新材料有限责任公司 | Titanium niobate coated hard carbon composite material and preparation method thereof |
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