CN109904435A - A kind of preparation method and combination electrode material of combination electrode material - Google Patents
A kind of preparation method and combination electrode material of combination electrode material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of combination electrode material and combination electrode materials.The preparation method of the combination electrode material is comprising steps of preparation LLOs@LATP composite material；CNTs is added in mixed acid solution and is heated, CNTs is then washed to neutrality, obtains the CNTs of acid processing；The CNTs of the acid processing is dispersed in alcohols solvent, the LLOs@LATP composite material is added, is then stirred by ultrasonic, by product ethanol washing, LLOs@LATP@CNTs composite material is obtained after drying.The present invention is by coating CNTs in LLOs@LATP composite material to which the combination electrode material with dual cladding structure be prepared, the electronic conductivity and ionic conductivity of electrode material entirety can be improved simultaneously, and then the problem of alleviating material capacity decaying, voltage decline, have the effect of that collaboration improves the chemical property of electrode material.
Description
Technical field
The present invention relates to electrode material field more particularly to the preparation methods and combination electrode material of a kind of combination electrode material
Material.
Background technique
As people are to the growing of energy demand and to the continuous of society and economy sustainable development understanding of importance
In-depth, the lithium ion battery with the characteristics of environmentally protective and efficient high energy are increasingly valued by people.Large and medium-sized electronic work
The application such as tool, energy-accumulating power station, electric vehicle, smart grid is to the energy density of lithium ion battery, safety, power density, circulation
Service life, price, environmental-friendly etc. are proposed requirements at the higher level.Wherein, the performance of anode material for lithium-ion batteries has become
Influence the deciding factor of entire battery energy density.Therefore, development capacity is high, have extended cycle life, the lithium of good rate capability from
Sub- cell positive material becomes current one of research hotspot.
The anode material for lithium-ion batteries of main commercialization is mainly LiCoO at this stage2, LiFePO4,
LiMnxNiyCo1-x-yO2(0 < x, y < 0.5) etc..LiCoO2Due to Co3+With toxicity, and cobalt is scarce resource, preparation cost
Height defines that it can be only applied to compact battery；LiFePO4Since intrinsic electronics and ionic conductivity is low, and pure phase
LiFePO4It is difficult to synthesize and LiFePO4Capacity and tap density be difficult to take into account；LiMnxNiyCo1-x-yO2Comprehensive LiCoO2、
LiMnO2And LNiO2The advantages of.But application requirement of the expansion in lithium ion battery applications field especially in terms of pure electric vehicle is high
Specific energy (300 Wh kg-1Or more) battery, therefore there is an urgent need to the lithium of high-energy-density material, especially height ratio capacity from
Sub- cell positive material.
Nearly stage, one kind are based on Li2MnO3Height ratio capacity (200-300 mAh g-1) positive electrode zLi2MnO3·(1-
z)LiMO2 (0<z<1, M=Mn0.5Ni0.5, MnxNiyCo1-x-y, 0 < x, y < 0.5) and (lithium-rich positive electrode), become full
One of the most promising material of this requirement of foot causes extensive pay close attention to and as research hotspot.But lithium-rich anode
Material there is a problem of it is several great urgently to be resolved, mainly in Li2MnO3In the activation of component, the irreversible release of oxygen,
Cause the layer structure of material to change to Spinel, and then causes discharge voltage decaying serious, and in high voltage cycle mistake
Cheng Zhong, the release of oxygen can accelerate the side reaction etc. between the decomposition and electrode and electrolyte of carbonic ester electrolyte, eventually lead to electricity
Tankage declines rapidly, while the lower conductivity of the material causes high rate performance poor, these seriously hinder its business
Change application.
In recent years, to solve the above-mentioned problems, researchers have carried out extensive work, 1. method of modifying, which specifically includes that, to be mixed
It is miscellaneous, such as Al, Cr；2. surface coats, such as Al2O3、Al(OH)3、AlPO4Deng preventing the dissolution of metal ion, inhibit side reaction
Generation, and then improve positive electrode capacity retention ratio；3. being pre-processed using inorganic acid or organic monoacid to material；④
Rich lithium material and deficient lithium carrier is compound, and when discharging for the first time, the lithium ion of irreversible abjection can be embedded in scarce lithium carrier, be dropped
Low irreversible capacity；5. particle nanosizing, comes into full contact with active material with electrolyte, shortens the diffusion path of lithium ion, mention
The high rate performance of high material.
Manthiram research group is by the past to LiCoO2The surface modifying method of positive electrode, uses Al2O3、
AlPO4, metal simple-substance Al, Al2O3-RuO2Covering material and graphite etc. are mixed respectively to lithium-rich positive electrode Li
[Li0.2Mn0.54Ni0.13Co0.13]O2Carry out surface coating modification.They have found that surface coating modification can be by material for the first time
Discharge capacity is from 250 mAh g-1Left and right is increased to 280 mAh g-1Left and right, irreversible capacity loss reduce 35-50 mAh g-1,
And the cycle performance and coulombic efficiency of material are also all improved.By comparing Al2O3、CeO2、ZrO2、SiO2、ZnO、AlPO4
Etc. covering materials and F-Adulterating influences the performance of positive electrode, they have found through Al2O3The material of cladding has preferably circulation
Performance, and pass through AlPO4The positive electrode of cladding then has lower first all irreversible capacity losses.
Also someone coats the performance for improving material by atomic layer deposition in recent years.Feng of Inst. of Physics, CAS
State star doctor is using Atomic layer deposition method in Li1.2Ni0.17Mn0.56Co0.07O2It is controllable that material surface deposits a layer thickness
Al2O3Layer, by the reversible capacity of electrode material from 200 mAh g-1It is increased to 250 mAh g-1, when coating thickness is less than 5 nm
When, surface coats Al2O3It can also inhibit the polarization of material.Surface is modified while improving the structural stability and cyclicity of material
Energy.
Surface cladding is one of current raising most widely used method of lithium-rich positive electrode chemical property.In recent years
Come, to the surface coating modification of lithium-rich positive electrode in addition to using common metal oxide (Al2O3、TiO2Deng), phosphoric acid
Salt (AlPO4、CoPO4Deng), outside carbon, pass through lithium ion conductor (LiAlO2Deng) its surface coating modification is being risen.Pass through
Surface cladding mitigates corrosion of the electrolyte to electrode material surface, reinforcing material structural stability, meanwhile, surface is modified can also be with
Electronic conductivity (carbon) or ionic conductivity (lithium ion conductor) are improved, electrode material high rate performance is improved.But it is most of general
Logical metal oxide (Al2O3、TiO2Deng) itself electronic conductivity and ionic conductivity it is low, lithium ion conductor (LiAlO2
Deng) electronic conductivity it is low, and the ionic conductivity of common carbon-coating is low, when the material for using these single is as clad
Can not achieve the effect that enhance electronic conductivity and ionic conductivity simultaneously, can inhibit instead material electronic conductivity or from
Electron conductivity, thus cannot more preferably chemical property.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of preparation methods of combination electrode material
And combination electrode material, it is intended to solve the presence of the electronic conductivity that cannot enhance electrode material simultaneously in existing surface coating technology
And ionic conductivity, so as to cause the not high problem of chemical property.
A kind of preparation method of combination electrode material, wherein comprising steps of
Prepare LLOs@LATP composite material；
CNTs is added in mixed acid solution and is heated, CNTs is then washed to neutrality, obtains the CNTs of acid processing；
The CNTs of the acid processing is dispersed in alcohols solvent, the LLOs@LATP composite material is added, then carries out ultrasound
Stirring, by product ethanol washing, obtains LLOs@LATP@CNTs composite material after drying.
The preparation method of the combination electrode material, wherein the preparation LLOs@LATP composite material comprising steps of
Lithium nitrate, aluminum nitrate, butyl titanate, ammonium dihydrogen phosphate are added in aqueous citric acid solution, stirring to solution becomes clear
Clearly, the precursor sol of titanium phosphate aluminium lithium is obtained；
Lithium-rich oxide is added into the precursor sol of the titanium phosphate aluminium lithium, before evaporation solvent obtains LLOs@LATP
Body is driven, obtains LLOs@LATP composite material through high-temperature calcination.
The preparation method of the combination electrode material, wherein the mixed acid solution is the mixed liquor of sulfuric acid and nitric acid.
The preparation method of the combination electrode material, wherein be dispersed in alcohols in the CNTs by the acid processing
Before in solvent further include: add dispersing agent in alcohols solvent.
The preparation method of the combination electrode material, wherein the alcohols solvent is ethyl alcohol, in ethylene glycol, butanol
It is a kind of.
The preparation method of the combination electrode material, wherein the dispersing agent is polyvinylpyrrolidone, dodecyl
One of benzene sulfonic acid sodium salt, lauryl sodium sulfate, cetyl polyoxyethylene ether sodium phosphate.
The preparation method of the combination electrode material, wherein the drying temperature is 60 ~ 90 DEG C.
The preparation method of the combination electrode material, wherein the temperature of the high-temperature calcination is 500 ~ 900 DEG C.
A kind of combination electrode material, wherein include: lithium-rich oxide, be coated on the lithium-rich oxide
Titanium phosphate aluminium lithium, the carbon nanotube that is coated on the titanium phosphate aluminium lithium.
The combination electrode material, wherein the mass percent of carbon nanotube described in the combination electrode material is 1
%~5 %。
The utility model has the advantages that
The present invention is using the fast-ionic conductor LATP of high ionic conductivity and the electronic conductor CNTs of highly electron conductive to rich lithium
Layered cathode material carries out double-coating, in the structure transformation and side reaction between electrolyte for inhibiting material, slows down electricity
While solving the oxygenolysis of liquid, the conductivity (electronic conductivity and ionic conductivity improve) of material entirety can be improved,
And then the problem of alleviating material capacity decaying, voltage decline, collaboration improves the chemical property of material.
Detailed description of the invention
Fig. 1 is the SEM figure of four kinds of electrode materials in present example 1.
Fig. 2 is the TEM figure of four kinds of electrode materials in present example 1.
Fig. 3 is the high rate performance figure of four kinds of electrode materials in present example 1.
Fig. 4 is the cycle performance figure under 0.2 C current density of four kinds of electrode materials in present example 1.
Specific embodiment
The present invention provides the preparation method and combination electrode material of a kind of combination electrode material, for make the purpose of the present invention,
Technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein
Specific embodiment is only used to explain the present invention, is not intended to limit the present invention.
The meaning of specific term, the meaning of English initialism in the present invention:
LLOs@LATP composite material, which represents, in the present invention is coated with titanium phosphate aluminium lithium on the surface of lithium-rich oxide.LLOs@
LATP@CNTs composite material, which is represented, is coated with carbon nanotube in LLOs@LATP composite material surface.
Compared to the ion insulating properties of common metal oxides, lithium ion conductor ionic conductivity with higher is being mentioned
The structural stability and thermal stability of high lithium-rich positive electrode inhibit the same of side reaction between positive electrode and electrolyte
When, it can be to avoid the transmission of the influence lithium ion after cladding, or even the diffusion rate of lithium ion can be improved, and then improve positive material
The chemical property of material.However, the low lithium ion conductor of electronic conductivity can inhibit electronics transfer.Solid electrolyte (fast ion
Conductor) as a kind of special lithium ion conductor, there is higher ionic conductivity, wherein glass ceramics [Li1+xAlxTi2-x
(PO4)3] (LATP, x=0.3-0.5) be NASICON type structure, at room temperature ionic conductivity be 10-4 S cm-1, it is a kind of
Good fast-ionic conductor；CNTs has special one-dimentional structure, then while itself possesses higher electronic conductivity,
It can accelerate lithium ion transport to a certain extent, therefore, using LATP lithium ion conductor and CNTs electronic conductor dual cladding
Lithium-rich oxide material, collaboration improve the chemical property of material.
The present invention provides a kind of preparation method of combination electrode material, comprising steps of
Prepare LLOs@LATP composite material；
CNTs is added in mixed acid solution and is heated, CNTs is then washed to neutrality, obtains the CNTs of acid processing；
The CNTs of the acid processing is dispersed in alcohols solvent, the LLOs@LATP composite material is added, then carries out ultrasound
Stirring, by product ethanol washing, obtains LLOs@LATP@CNTs composite material, that is to say combination electrode material after drying.
The present invention is by coating one layer of CNTs in LLOs@LATP composite material to be prepared with dual cladding structure
Combination electrode material.The dual cladding of both lithium ion conductor LATP and electronic conductor CNTs inhibits rich lithium layer in the present invention
Transformation of the slave stratiform of shape positive electrode LLOs to Spinel, improves the structural stability of material, slows down discharge voltage
Decaying.
Meanwhile the anticorrosive effect using covering material to electrolyte middle acid substance, it is coated by surface and reduces electrode
Contact area between material and electrolyte mitigates corrosion of the electrolyte to electrode material surface, inhibits electricity in charge and discharge process
The side reaction of pole material surface.
Moreover, CNTs has a degree of suction-operated to oxygen in the present invention, to alleviate carbonic ester under high voltage
The quickening of electrolyte is decomposed, and the stable circulation performance of material is improved.
The modified expansion that lithium ion and electronics has been respectively increased in the surface of both lithium ion conductor LATP and electronic conductor CNTs
Rate is dissipated, ionic conductivity and electronic conductivity is enhanced simultaneously in LLOs@LATP@CNTs composite material, improves material
Whole conductivity, improves the high rate performance of electrode material.The synergistic effect of both LATP and CNTs is so that LLOs@
LATP@CNTs composite material has peak capacity, most stable cycle performance and optimal high rate performance.
Preferably, the present invention also provides a kind of LLOs preparation methods, comprising steps of
By LiOH H2O、Mn(CH3COO3)2•4H2O、Ni(CH3COO3)2•4H2O、Co(CH3COO3)2•4H2O、H2C2O4(oxalic acid)
It is added in the aqueous solution of ethyl alcohol, 15-24 h, then the product water and ethanol washing that will obtain is heated at 150-200 DEG C, is connect
Dried at 70-100 DEG C, Li is prepared1.2Mn0.54Ni0.13Co0.13O2The precursor powder of (abbreviation LLOs)；
By the Li1.2Mn0.54Ni0.13Co0.13O2Precursor powder obtain LLOs through 500-900 DEG C of high-temperature calcination.
Preferably, the LiOH H2O、Mn(CH3COO3)2•4H2O、Ni(CH3COO3)2•4H2O、Co(CH3COO3)2•4H2O
The ratio between amount of substance is 1.2:0.54:0.13:0.13, that is to say the water that above-mentioned raw materials are added to ethyl alcohol according to stoichiometric ratio
In solution.
The preparation method of the LLOs is also a kind of liquid phase preparation process, and wherein solvent is the aqueous solution of ethyl alcohol.Preferably,
The ratio between amount of substance of ethyl alcohol and water is 1:1 in the aqueous solution of the ethyl alcohol.
Preferably, the preparation LLOs@LATP composite material comprising steps of
By lithium nitrate (LiNO3), aluminum nitrate (Al (NO3)3•9H2O), butyl titanate (Ti (OC4H9)4), ammonium dihydrogen phosphate
(NH4H2PO4) it is added to citric acid (C6H8O7) stir 0.5 ~ 3 h in aqueous solution, at 50 ~ 100 DEG C and become to solution and clarify, it obtains
The precursor sol of LATP；
Lithium-rich oxide is added into the precursor sol of the LATP, evaporation solvent obtains LLOs@LATP presoma, passes through
High-temperature calcination obtains LLOs@LATP composite material.
Preferably, solvent is evaporated by modes such as stirring, ball milling, ultrasounds, and controls the temperature 70 ~ 110 of evaporation solvent
℃.Further, the time being stirred is 3 ~ 8 h.The present invention, by using ball milling, stirs in evaporation dissolving agent process
It mixes, the methods of ultrasound realizes LATP to the cladding of LLOs.
Preferably, further include carrying out drying and processing after the evaporation solvent, remove remaining solvent.Wherein, the drying
The temperature of processing is 80 ~ 150 DEG C, and the drying and processing time is 5 ~ 14 h.
Preferably, the temperature of the high-temperature calcination is 500 ~ 900 DEG C, and the time of the high-temperature calcination is 3 ~ 7 h.This hair
It is bright so that LLOs LATP forerunner's precursor reactant is obtained LLOs LATP composite material by high-temperature calcination.
Preferably, the mixed acid solution is the mixed liquor of sulfuric acid and nitric acid.It is highly preferred that sulphur in the mixed acid solution
The volume ratio of acid and nitric acid is 1:3.Since the length of the CNTs without acid processing is longer, it is used directly to be coated, effect is not
It is very good.Therefore, the CNTs is carried out sour processing by the present invention, is prescinded, while more oxygen-containing group is generated on CNTs, and
The oxygen-containing group of generation can improve the chemical property of combination electrode material to a certain extent with adsorption of oxygen.
Preferably, before the CNTs by the acid processing is dispersed in alcohols solvent further include: in alcohols solvent
Middle addition dispersing agent.Wherein, the alcohols solvent is one of ethyl alcohol, ethylene glycol, butanol；The dispersing agent is polyethylene pyrrole
One of pyrrolidone (PVP), neopelex, lauryl sodium sulfate, cetyl polyoxyethylene ether sodium phosphate.
It is highly preferred that the dispersing agent is polyvinylpyrrolidone, the alcohols solvent is ethyl alcohol.The addition of dispersing agent of the present invention
It is and then to realize cladding to substrate more evenly in order to which CNTs can be preferably dispersed in alcohols solvent.
Preferably, it being obtained after the drying in LLOs@LATP@CNTs composite material, the drying temperature is 60 ~ 90 DEG C,
Make to remain in the ethyl alcohol on product quickly to volatilize.
The present invention also provides a kind of combination electrode materials, comprising: lithium-rich oxide is coated on the lithium-rich oxygen
Titanium phosphate aluminium lithium in compound, the carbon nanotube being coated on the titanium phosphate aluminium lithium.
Combination electrode material of the present invention can be prepared by above-mentioned preparation method.Meanwhile it is of the present invention
LLOs@LATP@CNTs composite material has porous spherical core-shell structure, is capable of the specific surface area of significant increase electrode material, into
And be conducive to improve the performances such as conductivity, cyclical stability, the specific capacity of combination electrode material.
Preferably, the mass percent of carbon nanotube described in the anode composite material is the % of 1 % ~ 5, at this time compound electric
Pole material has good chemical property.
As shown in Fig. 1 (a), LLOs is porous spherical structure, and this porous spherical structure is by a large amount of LLOs nano particles
It accumulates, the present invention coats CNTs again after porous spherical LLOs outer cladding LATP and forms two shell structure of a core.LATP conduct
Lithium ion conductor and CNTs cooperate with the conductivity for improving composite material as electronic conductor.And this porous spherical structure is formed
Three-dimensional structure, and LLOs is nano particle, thus therefore specific surface area with higher can be convenient for the insertion of lithium ion
And deintercalation.
Specifically, the duct communicated is formed in three-dimensional structure, these duct filling electrolytes are conducive to electrolyte
It penetrates into, electrolyte can come into full contact with material.The LLOs of particle nanosizing can shorten lithium ion diffusion path, basic herein
On, LATP can further improve the transmission of lithium ion, to improve the high rate performance of material.CNTs is located at the table of core-shell structure
Face can be conducive between two neighboring core-shell structure, the electron-transport between two neighboring three-dimensional structure, improve integral material
Electronic transmission performance.
Using two shell structure of a core, i.e. LLOs is successively wrapped by LATP and CNTs, is conducive to inhibit lithium ion insertion and take off
Crystal transition caused by during embedding, to improve the stability of material, cycle performance and coulombic efficiency.On this basis,
This three-dimensional structure is convenient for the conduction of heat, the especially CNTs positioned at surface that can be conducive to heat conduction, because without shape
At " hot spot ", material will not cause to fail because of overheat, to further improve the stability and cycle performance of material.
Embodiment 1
1. preparing LLOs material
By LiOH H2O、Mn(CH3COO3)2•4H2O、Ni(CH3COO3)2•4H2O、Co(CH3COO3)2•4H2O、H2C2O4For raw material,
It is added in the aqueous solution of ethyl alcohol (molar ratio of ethyl alcohol and water is 1:1), 20 h, then the product that will be obtained are heated at 175 DEG C
It with deionized water and ethanol washing, is dried at 85 DEG C, prepares Li1.2Mn0.54Ni0.13Co0.13O2Precursor powder, most pass through afterwards
750 DEG C of high-temperature calcinations obtain product LLOs material.
2. preparing LLOs@LATP composite material
By LiNO3、Al(NO3)3•9H2O、Ti(OC4H9)4、NH4H2PO4C is added6H8O7In aqueous solution, 5 h are stirred at 70 DEG C extremely
Solution becomes clarification, obtains Li1.4Al0.4Ti1.6(PO4)3The precursor sol of (abbreviation LATP) adds lithium-rich positive electrode
Li1.2Mn0.54Ni0.13Co0.13O2(abbreviation LLOs), 90 DEG C of 5 h of stirring evaporate solvent, and 10 h are dried at 100 DEG C, are obtained
LLOs LATP presoma most obtains LLOs LATP composite material through 700 DEG C of 5 h of high-temperature calcination afterwards.
3. preparing LLOs@CNTs composite material
With mixed acid (sulfuric acid and nitric acid volume ratio 1:3 in mixed acid) heat treatment CNTs, it is then washed to neutrality, obtains sour place
The CNTs of reason.Again using PVP as dispersing agent, ethyl alcohol is solvent, stirs the CNTs of ultrasound difference 40 min dispersion acid processing, richness is added
Lithium layered cathode material LLOs continues ultrasonic agitation 40 min respectively, finally uses ethanol washing, and 70 DEG C of drying obtain LLOs
CNTs composite material.
4. preparing LLOs@LATP@CNTs composite material
With mixed acid (sulfuric acid and nitric acid volume ratio 1:3 in mixed acid) heat treatment CNTs, it is then washed to neutrality, obtains sour place
The CNTs of reason.Again using PVP as dispersing agent, ethyl alcohol is solvent, and step 2 is added in the CNTs of stirring 30 min of ultrasound dispersion acid processing
The LLOs@LATP of preparation continues ultrasonic agitation 30 min respectively, finally uses ethanol washing, and 70 DEG C of drying obtain LLOs@
LATP@CNTs composite material.
LLOs@LATP, LLOs@CNTs, LLOs@LATP@CNTs composite material and LLOs material are obtained to what is be prepared
Material is characterized.
Fig. 1,2 are respectively that the SEM figure of four kinds of electrode materials in this example and TEM scheme.In Fig. 1 and Fig. 2, figure (a) is LLOs,
Scheming (b) is LLOs@CNTs, and figure (c) is LLOs@LATP, and figure (d) is LLOs@[email protected]. 3 is four kinds of electricity in this example
The high rate performance figure of pole material.Fig. 4 is cycle performance figure of four kinds of electrode materials under 0.2 C current density in this example.
SEM figure and TEM figure in Fig. 1-2 sufficiently show LLOs@CNTs, LLOs@LATP, LLOs@LATP@CNTs tri-
Covering material in kind composite material is evenly distributed on the surface matrix LLOs.Four kinds of electrode material high rate performance figures of Fig. 3-4 and
It is forthright with optimal times that cycle performance figure under 0.2 C current density shows LLOs LATP CNTs composite material respectively
There can be large increase compared to the chemical property of unmodified LLOs material with highest capacity, most stable of cycle performance.
Table 1 is the specific surface area data of the preparation-obtained four kinds of materials of the present embodiment.As can be seen from Table 1: with it is other
Three kinds of materials are compared, and the specific surface area of LLOs@LATP@CNTs is maximum.In conjunction with Fig. 1 and Fig. 2, LLOs@prepared by the present invention
LATP@CNTs composite material has porous spherical structure, while porous spherical structure combines the double-deck packet that the composite material has
The core-shell structure covered is capable of the specific surface area of composite material prepared by significant increase, is conducive to improve combination electrode material
The performances such as mass transfer, heat transfer, so that composite material exhibits be made to go out the high feature of conductivity height, good cycling stability, specific capacity.
Table 1, the specific surface area data of 1 preparation-obtained four kind of material of embodiment
Embodiment 2
1. preparing LLOs@LATP composite material
By LiNO3、Al(NO3)3•9H2O、Ti(OC4H9)4、NH4H2PO4C is added6H8O7In aqueous solution, 3 h are stirred at 50 DEG C extremely
Solution becomes clarification, obtains Li1.4Al0.4Ti1.6(PO4)3The precursor sol of (abbreviation LATP) adds lithium-rich positive electrode
Li1.2Mn0.54Ni0.13Co0.13O2(being prepared by embodiment 1), 70 DEG C of 8 h of stirring evaporate solvent, 14 h at 80 DEG C
Drying, obtains LLOs LATP presoma, most obtains LLOs LATP composite material through 600 DEG C of 6 h of high-temperature calcination afterwards.
2. preparing LLOs@LATP@CNTs composite material
With mixed acid (sulfuric acid and nitric acid volume ratio 1:3 in mixed acid) heat treatment CNTs, it is then washed to neutrality, obtains sour place
The CNTs of reason.Again using PVP as dispersing agent, ethyl alcohol is solvent, and step 1 is added in the CNTs of stirring 10 min of ultrasound dispersion acid processing
The product LLOs@LATP being prepared continues ultrasonic agitation 50 min respectively, finally uses ethanol washing, and 65 DEG C of drying obtain
LLOs@LATP@CNTs composite material.
Embodiment 3
1. preparing LLOs@LATP composite material
By LiNO3、Al(NO3)3•9H2O、Ti(OC4H9)4、NH4H2PO4C is added6H8O7In aqueous solution, 1 h is stirred at 90 DEG C extremely
Solution becomes clarification, obtains Li1.4Al0.4Ti1.6(PO4)3The precursor sol of (abbreviation LATP) adds lithium-rich positive electrode
Li1.2Mn0.54Ni0.13Co0.13O2(being prepared by example 1), 95 DEG C of 4 h of stirring evaporate solvent, and 6 h dry at 140 DEG C
It is dry, LLOs LATP presoma is obtained, most obtains LLOs LATP composite material through 850 DEG C of 4 h of high-temperature calcination afterwards.
2. preparing LLOs@LATP@CNTs composite material
With mixed acid (sulfuric acid and nitric acid volume ratio 1:3 in mixed acid) heat treatment CNTs, it is then washed to neutrality, obtains acid
The CNTs of processing.Again using PVP as dispersing agent, ethyl alcohol is solvent, and step is added in the CNTs of stirring 45 min of ultrasound dispersion acid processing
The LLOs@LATP of one preparation continues ultrasonic agitation 45 min respectively, finally uses ethanol washing, and 80 DEG C of drying obtain LLOs@
LATP@CNTs composite material.
The present invention is based on the anode material for lithium-ion batteries of height ratio capacity-lithium-rich positive electrodes in charge and discharge process
The problem of side reaction, crystal transition, oxygen loss etc. cause capacity attenuation, voltage to decline occurs with electrolyte, using macroion electricity
The electronic conductor CNTs of the fast-ionic conductor of conductance-solid electrolyte LATP and highly electron conductive carries out the positive electrode double
Layer cladding, while inhibiting the side reaction between the structure transformation of material and electrolyte, slowing down the oxygenolysis of electrolyte,
Can be improved the conductivity (electronic conductivity and ionic conductivity improve) of material entirety, so alleviate material capacity decaying,
The problem of voltage declines, promotes the chemical property of material.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of combination electrode material, which is characterized in that comprising steps of
Prepare LLOs@LATP composite material；
CNTs is added in mixed acid solution and is heated, CNTs is then washed to neutrality, obtains the CNTs of acid processing；
The CNTs of the acid processing is dispersed in alcohols solvent, the LLOs@LATP composite material is added, then carries out ultrasound
Stirring, by product ethanol washing, obtains LLOs@LATP@CNTs composite material after drying.
2. the preparation method of combination electrode material according to claim 1, which is characterized in that the preparation LLOs@LATP
Composite material comprising steps of
Lithium nitrate, aluminum nitrate, butyl titanate, ammonium dihydrogen phosphate are added in aqueous citric acid solution, stirring to solution becomes clear
Clearly, the precursor sol of titanium phosphate aluminium lithium is obtained；
Lithium-rich oxide is added into the precursor sol of the titanium phosphate aluminium lithium, before evaporation solvent obtains LLOs@LATP
Body is driven, obtains LLOs@LATP composite material through high-temperature calcination.
3. the preparation method of combination electrode material according to claim 1, which is characterized in that the mixed acid solution is sulphur
The mixed liquor of acid and nitric acid.
4. the preparation method of combination electrode material according to claim 1, which is characterized in that handle the acid described
CNTs be dispersed in alcohols solvent before further include: dispersing agent is added in alcohols solvent.
5. the preparation method of combination electrode material according to claim 1 or 4, which is characterized in that the alcohols solvent is
One of ethyl alcohol, ethylene glycol, butanol.
6. the preparation method of combination electrode material according to claim 4, which is characterized in that the dispersing agent is polyethylene
One of pyrrolidones, neopelex, lauryl sodium sulfate, cetyl polyoxyethylene ether sodium phosphate.
7. the preparation method of combination electrode material according to claim 1, which is characterized in that the drying temperature be 60 ~
90 ℃。
8. the preparation method of combination electrode material according to claim 2, which is characterized in that the temperature of the high-temperature calcination
It is 500 ~ 900 DEG C.
9. a kind of combination electrode material characterized by comprising lithium-rich oxide is coated on the lithium-rich oxidation
Titanium phosphate aluminium lithium on object, the carbon nanotube being coated on the titanium phosphate aluminium lithium.
10. combination electrode material according to claim 9, which is characterized in that carbon described in the combination electrode material is received
The mass percent of mitron is the % of 1 % ~ 5.
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