CN110061234A - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN110061234A CN110061234A CN201910446186.6A CN201910446186A CN110061234A CN 110061234 A CN110061234 A CN 110061234A CN 201910446186 A CN201910446186 A CN 201910446186A CN 110061234 A CN110061234 A CN 110061234A
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of anode material for lithium-ion batteries and preparation method thereof, belong to positive electrode field.Anode material for lithium-ion batteries provided by the invention is core-shell structure, is made of core and clad；The core includes doping vario-property LiMn2O4 and carbon nanotube, and the carbon nanotube three-dimensional contact consolidation doping vario-property LiMn2O4 forms micron-size spherical material；The clad includes two-phase flexible polymer.Anode material for lithium-ion batteries provided by the invention has excellent cyclical stability and big high rate performance, and after recycling 200 times, capacity retention ratio may be up to 98.9%；And anode material for lithium-ion batteries provided by the invention still has big specific discharge capacity under high magnification, and when rate of charge increases to 30C by 0.5C, first discharge specific capacity conservation rate is 84.5%.
Description
Technical field
The present invention relates to positive electrode fields more particularly to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technique
With spinel-type LiMn2O4As anode material for lithium-ion batteries is high with voltage platform, thermal stability is good, manganese money
Source is abundant, technology of preparing is mature, production cost is low, has a safety feature and the advantages of no pollution to the environment.With LiFePO4 with
And ternary material is compared, the synthesis sexual valence of the material is relatively high, has cost advantage outstanding.
However, LiMn2O4Mn in positive electrode3+Jahn-Teller effect, in oxygen defect and electrolyte manganese dissolution
Problem, to LiMn2O4Structural stability and lithium ion diffusion produce serious influence, lead to LiMn2O4Positive electrode is in charge and discharge
There are cyclical stabilities in electric process it is poor, multiplying power is low the problems such as, restrict the large-scale commercial application of the material.
Summary of the invention
The present invention provides a kind of anode material for lithium-ion batteries, anode material for lithium-ion batteries provided by the invention has
The characteristics of high rate capability is superior and good cycling stability.
The present invention provides a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries is core-shell structure,
It is made of core and clad；The core includes doping vario-property LiMn2O4 and carbon nanotube, the carbon nanotube three-dimensional contact
It consolidates doping vario-property LiMn2O4 and forms micron-size spherical material；The clad includes two-phase flexible polymer.
The chemical formula of the doping vario-property LiMn2O4 is LiMn2-xMxO4, 0 x≤0.1 <；The M be Mg, Zn, Cu, Ni,
Co, Cr, Al, Ga, In, Tl, Ti, Si or Zr；
The two-phase flexible polymer includes polyethylene glycol and conducting polymer；The conducting polymer include polypyrrole,
Polyaniline or polyethylene dioxythiophene.
Preferably, the doping vario-property LiMn2O4 accounts for the 90~97% of core quality.
Preferably, the diameter of the core is 10~20 μm；The clad with a thickness of 5~20nm.
Preferably, the inside of the clad is conducting polymer；The outside of the clad is polyethylene glycol.
Preferably, the mass ratio of the polyethylene glycol and conducting polymer is 0.5~2:1.
The present invention provides the preparation methods of anode material for lithium-ion batteries described in above-mentioned technical proposal, including following step
It is rapid:
(1) stoichiometrically the source Li, the source Mn and dopant are mixed, obtains mixed slurry；The dopant includes Mg
Source, the source Zn, the source Cu, the source Ni, the source Co, the source Cr, the source Al, the source Ga, the source In, the source Tl, the source Ti, the source Si or the source Zr；
The mixed slurry is successively dried, pre-burning and the processing of whole burning, obtains doping vario-property LiMn2O4；
(2) the doping vario-property LiMn2O4 that the step (1) obtains is refined, obtains nanoscale doping vario-property mangaic acid
Lithium；
(3) it pelletizes, obtains after mixing nanoscale doping vario-property LiMn2O4 and carbon nanotube that the step (2) obtains
To the micron-size spherical core based on carbon nanotube three-dimensional contact consolidation；
(4) it disperses the core that conducting polymer monomer, dopant and step (3) are prepared in dehydrated alcohol, so
After be added oxidant, carry out oxidation polymerization, obtain intermediate product；
(5) disperse the intermediate product that the step (4) obtains in polyglycol solution, remove solvent after obtain lithium from
Sub- cell positive material.
Preferably, the temperature of pre-burning is 400~450 DEG C in the step (1), and the time is 4~6h；The temperature burnt eventually
It is 750~825 DEG C, the time is 12~18h.
Preferably, the method pelletized in the step (3) is water-based spray granulation, and the environment temperature of the granulation is
120~200 DEG C.
Preferably, dopant includes paratoluenesulfonic acid sodium salt, dodecyl benzene sulfonic acid, camphorsulfonic acid, salt in the step (4)
One of acid and dodecyl sodium sulfate are a variety of；The oxidant includes ferric trichloride, ferric perchlorate, ammonium persulfate and mistake
One of hydrogen oxide is a variety of；The temperature of the oxidation polymerization is 3~5 DEG C, and the time is 5~10h.
Preferably, the concentration of polyglycol solution is 0.5~2mol/L in the step (5).
The present invention provides a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries is core-shell structure,
It is made of core and clad；The core includes doping vario-property LiMn2O4 and carbon nanotube, the carbon nanotube three-dimensional contact
It consolidates doping vario-property LiMn2O4 and forms micron-size spherical material；The clad includes two-phase flexible polymer；The doping changes
Property LiMn2O4 chemical formula be LiMn2-xMxO4, 0 x≤0.1 <；The M be Mg, Zn, Cu, Ni, Co, Cr, Al, Ga, In, Tl,
Ti, Si or Zr；The polymer includes polyethylene glycol and conducting polymer；The conducting polymer includes polypyrrole, polyaniline
Or polyethylene dioxythiophene.
The present invention is doped modification to LiMn2O4 by the way of foreign cation, is effectively reducing lithium ion battery just
The Jahn-Teller effect and oxygen defect of pole material, improve the structural stability of material；The addition of carbon nanotube can not only
Play the role of nano particle of three-dimensional contact consolidation, it is more firm to make core structure, and can also increase substantially lithium from
The electronic conductivity of sub- cell positive material；Polymer covering layer effectively completely cuts off contact of the active material with electrolyte, inhibits
The dissolution of manganese, and polymer have flexility buffering repeated charge during material volume change, reinforcing material
Structural stability, while polymer covering layer can ensure the high-speed conduction of electronics and lithium ion.Embodiment the result shows that,
Anode material for lithium-ion batteries provided by the invention has excellent cyclical stability and big high rate performance, after recycling 200 times, holds
Amount conservation rate may be up to 98.9%；And anode material for lithium-ion batteries provided by the invention still has big under high magnification
Specific discharge capacity, when rate of charge increases to 30C by 0.5C, first discharge specific capacity conservation rate is 84.5%.
Detailed description of the invention
Fig. 1 is the experiment flow figure of embodiment 1；
Fig. 2 is the SEM figure for the anode material for lithium-ion batteries that embodiment 1 is prepared；
Fig. 3 is the cyclical stability figure for the anode material for lithium-ion batteries that embodiment 1 is prepared；
Fig. 4 is the high rate performance figure for the anode material for lithium-ion batteries that embodiment 2 is prepared.
Specific embodiment
The present invention provides a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries is core-shell structure,
It is made of core and clad；The core includes doping vario-property LiMn2O4 and carbon nanotube, the carbon nanotube three-dimensional contact
It consolidates doping vario-property LiMn2O4 and forms micron-size spherical material；The clad includes two-phase flexible polymer；
The chemical formula of the doping vario-property LiMn2O4 is LiMn2-xMxO4, 0 x≤0.1 <；The M be Mg, Zn, Cu, Ni,
Co, Cr, Al, Ga, In, Tl, Ti, Si or Zr；
The two-phase flexible polymer includes polyethylene glycol and conducting polymer；The conducting polymer include polypyrrole,
Polyaniline or polyethylene dioxythiophene.
In the present invention, the anode material for lithium-ion batteries is core-shell structure, is made of core and clad.In this hair
In bright, the core includes doping vario-property LiMn2O4 and carbon nanotube, the carbon nanotube three-dimensional contact consolidation doping vario-property manganese
Sour lithium forms micron-size spherical material；The carbon nanotube preferably includes multi-walled carbon nanotube, single-walled carbon nanotube or graphene
Pipe.In core of the present invention, doping vario-property LiMn2O4 preferably accounts for the 90~97% of core quality, further preferably 90~
95%.In the present invention, the addition of the carbon nanotube can not only play the work of three-dimensional contact consolidation doping vario-property LiMn2O4
With it is more firm making core structure, and the electronic conductivity of anode material for lithium-ion batteries can also be increased substantially.In this hair
In bright, the diameter of the core is preferably 10~20 μm, further preferably 12~18 μm, more preferably 14~16 μm.
In the present invention, the clad includes two-phase flexible polymer, and the inside of the clad is preferably conductive poly-
Close object；The outside of the clad is preferably polyethylene glycol.In the present invention, the quality of the polyethylene glycol and conducting polymer
Than being preferably 0.5~2:1, further preferably 1.0~1.5:1.In the present invention, the conducting polymer is conducive to improve lithium
The electric conductivity of ion battery positive electrode.The clad is preferably provided to two layers of polymers structure by the present invention, can be effective
Ground completely cuts off contact of the active material with electrolyte, inhibits the dissolution of manganese, and the flexility buffering that polyethylene glycol has is repeatedly
The volume change of material in charge and discharge process, the structural stability of reinforcing material.In the present invention, the thickness of the clad is excellent
It is selected as 5~20nm, further preferably 10~15nm.
The present invention also provides the preparation methods of above-mentioned anode material for lithium-ion batteries, comprising the following steps:
(1) stoichiometrically the source Li, the source Mn and dopant are mixed, obtains mixed slurry；The dopant includes Mg
Source, the source Zn, the source Cu, the source Ni, the source Co, the source Cr, the source Al, the source Ga, the source In, the source Tl, the source Ti, the source Si or the source Zr；
The mixed slurry is successively dried, pre-burning and the processing of whole burning, obtains doping vario-property LiMn2O4；
(2) the doping vario-property LiMn2O4 that the step (1) obtains is refined, obtains nanoscale doping vario-property mangaic acid
Lithium；
(3) it pelletizes, obtains after mixing nanoscale doping vario-property LiMn2O4 and carbon nanotube that the step (2) obtains
To the micron-size spherical core based on carbon nanotube three-dimensional contact consolidation；
(4) it disperses the core that conducting polymer monomer, dopant and step (3) are prepared in dehydrated alcohol, so
After be added oxidant, carry out oxidation polymerization, obtain intermediate product；
(5) disperse the intermediate product that the step (4) obtains in polyglycol solution, remove solvent after obtain lithium from
Sub- cell positive material.
The present invention stoichiometrically mixes the source Li, the source Mn and dopant, obtains mixed slurry；By the mixed slurry
It is successively dried, pre-burning and the processing of whole burning, obtains doping vario-property LiMn2O4.
In the present invention, the dopant includes the source Mg, the source Zn, the source Cu, the source Ni, the source Co, the source Cr, the source Al, the source Ga, In
Source, the source Tl, the source Ti, the source Si or the source Zr.In the present invention, the lithium source preferably includes lithium carbonate, lithium acetate, lithium nitrate, lemon
One of sour lithium, lithium oxalate and lithium hydroxide are a variety of；The source Mn preferably includes manganese dioxide, manganese sesquioxide managnic oxide, four oxygen
Change one of three manganese, hydroxyl manganese oxide, manganese acetate, manganese carbonate, manganese nitrate and manganese oxalate or a variety of；The manganese dioxide is preferred
For electrolytic manganese dioxide.After the present invention preferably mixes the source Li, the source Mn and dopant, wet ball grinding is carried out in dehydrated alcohol,
In the present invention, the revolving speed of the wet ball grinding is preferably 300~400r/min, and the time is preferably 3~8h.The present invention is by grinding
Mill is sufficiently mixed the source Li, the source Mn and dopant.
After the completion of mixing, the mixed slurry is successively dried the present invention, pre-burning and whole burning are handled, and obtains doping and changes
Property LiMn2O4.In the present invention, the temperature of the drying is preferably 80~110 DEG C；The temperature of the pre-burning is preferably 400~
450 DEG C, the time is preferably 4~6h；The temperature burnt eventually is preferably 750~825 DEG C, and the time is preferably 12~18h.
After obtaining doping vario-property LiMn2O4, the present invention refines doping vario-property LiMn2O4, obtains nanoscale doping and changes
Property LiMn2O4.In the present invention, the mode of the refinement is preferably wet ball grinding, and the solvent of the wet ball grinding is preferably anhydrous
Ethyl alcohol, the revolving speed of the wet ball grinding are preferably 300~400r/min, and the time is preferably 5~15h.The present invention preferably passes through wet
Doping vario-property LiMn2O4 is ground into nano-scale by method ball milling, obtains nanoscale doping vario-property LiMn2O4.
After obtaining nanoscale doping vario-property LiMn2O4, the present invention mixes nanoscale doping vario-property LiMn2O4 and carbon nanotube
After pelletize, obtain based on carbon nanotube three-dimensional get in touch with consolidation micron-size spherical core.Present invention preferably employs water base sprays
Mist granulation is pelletized, and the present invention does not specially require the specific embodiment of water-based spray granulation, using this field
Known to technical staff.In the present invention, the environment temperature of the granulation is preferably 120~200 DEG C, further preferably
It is 140~180 DEG C.In the present invention, the addition of the carbon nanotube can not only play three-dimensional contact consolidation nanoscale doping
Modified lithium manganate particle, avoids nanoparticle agglomerates, and the grain structure for obtaining water-based spray granulation is more firm, but also
The electronic conductivity for the anode material for lithium-ion batteries being finally prepared can be increased substantially.
After the completion of granulation, powder is obtained, the present invention is preferably dried powder, obtains three-dimensional based on carbon nanotube
Get in touch with the micron-size spherical core of consolidation.In the present invention, the temperature of the drying is preferably 100~300 DEG C, further preferably
It is 105~200 DEG C, more preferably 150 DEG C.
After obtaining core, the present invention disperses conducting polymer monomer, dopant and core in dehydrated alcohol, then plus
Enter oxidant, carries out oxidation polymerization, obtain intermediate product.
In the present invention, the dopant preferably includes paratoluenesulfonic acid sodium salt, dodecyl benzene sulfonic acid, camphorsulfonic acid, salt
One of acid and dodecyl sodium sulfate are a variety of；The oxidant preferably includes ferric trichloride, ferric perchlorate, ammonium persulfate
With one of hydrogen peroxide or a variety of；The conducting polymer monomer preferably includes pyrroles, aniline or ethene dioxythiophene.?
In the present invention, the molar ratio of the conducting polymer monomer and dopant is preferably 3:1；The conducting polymer monomer and oxidation
The molar ratio of agent is preferably 1:1, and the temperature of the oxidation polymerization is preferably 3~5 DEG C, and the time is preferably 5~10h；The oxidation
The pH value of polymerization reaction is preferably 3.8~4.2, further preferably pH=4.In the present invention, conducting polymer monomer is in oxygen
Under the action of agent and dopant, polymerization reaction, concrete principle are as follows: with the presence of oxidant in system occur for conducting polymer monomer
When, it can be oxidized under the action of oxidant in a conducting polymer monomer molecule of electroneutral and lose an electronics, become
Radical cation；Latter two right radical cation collides in system to be combined into containing there are two double sun of radical cation
Ion dimer, dication dimer at this time generate a dimer in electroneutral by disproportionation in system；
The dimer of electroneutral can be combined with each other with the radical cation in system again and generate the radical cation of tripolymer, pass through
Disproportionation and generate the tripolymer in electroneutral, ultimately generated the conducting polymer of long chain in cycles.
After the completion of oxidative polymerization, preferably oxidative polymerization product is dried by the present invention, obtains intermediate product.
In the present invention, the temperature of the drying is preferably 80~110 DEG C.
The present invention generates conducting polymer by oxidative polymerization, and conducting polymer is coated with core, forms intermediate produce
Object.In the present invention, the conducting polymer is conducive to improve the electric conductivity of anode material for lithium-ion batteries.
After obtaining intermediate product, the present invention disperses intermediate product in polyglycol solution, obtains lithium after removing solvent
Ion battery positive electrode.In the present invention, the solvent of the polyglycol solution is preferably deionized water and/or N- methyl pyrrole
Pyrrolidone, the concentration of the polyglycol solution are preferably 1~1.5mol/L.The present invention is preferably evaporated by way of stirring
Solvent, the temperature of the stirring are preferably 50~80 DEG C, and the time is preferably 0.5~5h.The lithium ion battery that the present invention obtains is just
In the material of pole, coated with polyethylene glycol is on the surface of intermediate product.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
Embodiment 1 prepares the flow chart of anode material for lithium-ion batteries as shown in Figure 1, preparing lithium according to method shown in Fig. 1
Ion battery positive electrode.
By aluminum nitrate, electrolytic manganese dioxide and lithium carbonate according to Li, Mn and Al molar ratio be 1.05:1.95:0.05
Mixing, under the action of dehydrated alcohol grinding aid and wet ball grinding 3h.After to ball milling, obtained mixed slurry is shifted
It is dried into evaporating dish.Finally, dry mixture grinding is uniformly placed on 450 DEG C of pre-burning 4h in Muffle furnace, again
Grinding is placed on 800 DEG C of whole 12h that burn in Muffle furnace and obtains LiMn1.95Al0.05O4。
Using ball-milling technology by the LiMn of preparation1.95Al0.05O4Crushing is nano-scale particle, and dispersing agent is dehydrated alcohol, is turned
Speed is 300r/min, time 10h.Then by the resulting nano-scale particle of 10g and 1g multi-walled carbon nanotube (being abbreviated as MWCNT)
Mixing is added 15mL deionized water, obtained solution is spray-dried under the conditions of 180 DEG C and obtains core LiMn1.95Mg0.05O4@
MWCNT, and it is dry under the conditions of 150 DEG C of temperature.
Dopant paratoluenesulfonic acid sodium salt and 0.3g pyrrole monomer are dispersed in dehydrated alcohol to (pyrrole monomer and to first
The molar ratio of benzene sulfonic acid sodium salt is 3:1), and it is added under conditions of continuing magnetic force stirring that 10g is above-mentioned obtains core, it obtains suspended
Liquid；Then by the oxidant FeCl with pyrrole monomer equimolar amounts3·6H2O is added dropwise in above-mentioned suspension, in ice-water bath
6h is persistently stirred under environment and completes oxidation polymerization process, completes the cladding of electronic conductor clad polypyridine (being abbreviated as PPy).Most
It disperses the Aqueous Solutions of Polyethylene Glycol (being abbreviated as PEG) that 0.3g concentration is 1mol/L again by the above-mentioned covering material of acquisition afterwards
In, magnetic agitation under 60 DEG C of water baths is until solvent evaporates to obtain target material LiMn1.95Al0.05O4@MWCNT@PPy-
PEG。
The LiMn that embodiment 1 is prepared1.95Al0.05O4@MWCNT@PPy-PEG is scanned electron microscope analysis, as a result such as
Shown in Fig. 2.
LiMn prepared by embodiment 11.95Al0.05O4@MWCNT@PPy-PEG carries out constant current charge-discharge test, by testing
As a result it is found that under 55 DEG C of hot environments, when charge-discharge magnification is 0.5C, the electric discharge for the first time of the anode material for lithium-ion batteries
Specific capacity can reach 126.5mAh/g.LiMn prepared by embodiment 11.95Al0.05O4@MWCNT@PPy-PEG carries out cycle performance
Test, test results are shown in figure 3.From the figure 3, it may be seen that the anode material for lithium-ion batteries has excellent stable circulation performance,
It still can reach 124.9mAh/g after circulation 200 times, capacity retention ratio is up to 98.7%.
Embodiment 2
By magnesium nitrate, mangano-manganic oxide and lithium hydroxide according to Li, Mn and Mg molar ratio be 1.05:1.95:0.05
Mixing, under the action of dehydrated alcohol grinding aid and wet ball grinding 3h.After to ball milling, obtained mixed slurry is shifted
It is dried into evaporating dish.Finally, dry mixture grinding is uniformly placed on 400 DEG C of pre-burning 6h in Muffle furnace, again
Grinding is placed on 780 DEG C of whole 15h that burn in Muffle furnace and obtains LiMn1.95Mg0.05O4。
Using ball-milling technology by the LiMn of preparation1.95Mg0.05O4Crushing is nano-scale particle, and dispersing agent is dehydrated alcohol, is turned
Speed is 300r/min, time 10h.Then the resulting nano-scale particle of 12g and 1gMWCNT are mixed, 15mL deionization is added
Obtained solution is spray-dried under the conditions of 180 DEG C and obtains core LiMn by water1.95Mg0.05O4@MWCNT, and in 150 DEG C of temperature
Under the conditions of it is dry.
It disperses above-mentioned core material in suitable deionized water, the aniline of 0.3g is added, and continue stirring 30 minutes.
Then, hydrochloric acid is added dropwise, the pH value for adjusting solution is 4, and the solution is transferred in ice-water bath.It is added dropwise under nitrogen atmosphere suitable
Gained sediment is successively used deionized water, dehydrated alcohol and acetone more by the ammonium persulfate of amount after reacting 6h in ice-water bath
Secondary washing, and in 80 DEG C of dryings, complete the cladding of electronic conductor clad PANI.Finally again by the above-mentioned covering material of acquisition
It is scattered in the solution of 0.3g polyethylene glycol, magnetic agitation under 60 DEG C of water baths is until solvent evaporates to obtain target material
LiMn1.95Mg0.05O4@MWCNT@PANI-PEG。
LiMn prepared by the present embodiment 21.95Mg0.05O4@MWCNT@PANI-PEG anode material for lithium-ion batteries carries out permanent
Current charge-discharge electrical testing, test results are shown in figure 4.By test result it is found that the anode material for lithium-ion batteries is with excellent
Big high rate performance, when rate of charge be 0.5C when, the first discharge specific capacity that discharge-rate is 0.5C is 125.8mAh/g, and
Discharge-rate is that the specific discharge capacity of 30C can reach 106.3mAh/g, maintains the 84.5% of first discharge specific capacity.
Embodiment 3
By nano-titanium dioxide, electrolytic manganese dioxide and lithium carbonate according to Li, Mn and Ti molar ratio be 1.05:
1.95:0.05 mixing, under the action of dehydrated alcohol grinding aid and wet ball grinding 10h.It is mixed by what is obtained after to ball milling
Conjunction slurry, which is transferred in evaporating dish, to be dried.Finally, by dry mixture grinding be uniformly placed in Muffle furnace 450 DEG C it is pre-
6h is burnt, regrinding is placed on 780 DEG C of whole 15h that burn in Muffle furnace and obtains LiMn1.95Ti0.05O4。
Using ball-milling technology by the LiMn of preparation1.95Ti0.05O4Crushing is nano-scale particle, and dispersing agent is dehydrated alcohol, is turned
Speed is 300r/min, time 10h.Then the resulting nano-scale particle of 25g and 2gMWCNT are mixed, 30mL deionization is added
Water, by obtained solution, spraying granulation obtains core LiMn under the conditions of 180 DEG C1.95Ti0.05O4@MWCNT particle, and at 150 DEG C
It is dry under the conditions of temperature.
Dopant paratoluenesulfonic acid sodium salt and 0.3g pyrrole monomer are dispersed in dehydrated alcohol to (pyrrole monomer and to first
The molar ratio of benzene sulfonic acid sodium salt is 3:1), and the above-mentioned core material of 10g is added under conditions of continuing magnetic force stirring, it obtains suspended
Liquid；Then by the oxidant FeCl with pyrrole monomer equimolar amounts3·6H2O is added dropwise in above-mentioned suspension, lasting to stir
6h completes oxidation polymerization process, completes the cladding of electronic conductor clad polypyridine.Finally again by the above-mentioned covering material of acquisition
Secondary to be scattered in the solution of 0.3gPEG, magnetic agitation under 60 DEG C of water baths is until solvent evaporates to obtain target material
LiMn1.95Ti0.05O4@MWCNT@PPy-PEG。
LiMn prepared by the present embodiment 31.95Ti0.05O4@MWCNT@PPy-PEG anode material for lithium-ion batteries carries out permanent
Current charge-discharge electrical testing.By test result it is found that the anode material for lithium-ion batteries has excellent stable circulation performance.55
Under DEG C hot environment, when charge-discharge magnification is 0.5C, the first discharge specific capacity of the anode material for lithium-ion batteries be can reach
126.1mAh/g still can reach 124.7mAh/g after recycling 200 times, and capacity retention ratio is up to 98.9%.
To sum up, anode material for lithium-ion batteries good cycling stability provided by the invention, after loop test 200 times, capacity
Conservation rate is 98.7%~98.9%；And anode material for lithium-ion batteries provided by the invention still has greatly under high magnification
Specific discharge capacity, when rate of charge increases to 30C by 0.5C, first discharge specific capacity conservation rate be 84.5%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries is core-shell structure, by core and clad
Composition；The core includes doping vario-property LiMn2O4 and carbon nanotube, the carbon nanotube three-dimensional contact consolidation doping vario-property manganese
Sour lithium forms micron-size spherical material；The clad includes two-phase flexible polymer.
The chemical formula of the doping vario-property LiMn2O4 is LiMn2-xMxO4, 0 x≤0.1 <；The M be Mg, Zn, Cu, Ni, Co, Cr,
Al, Ga, In, Tl, Ti, Si or Zr；
The two-phase flexible polymer includes polyethylene glycol and conducting polymer；The conducting polymer includes polypyrrole, polyphenyl
Amine or polyethylene dioxythiophene.
2. anode material for lithium-ion batteries according to claim 1, which is characterized in that the doping vario-property LiMn2O4 accounts for core
The 90~97% of core quality.
3. anode material for lithium-ion batteries according to claim 1, which is characterized in that the diameter of the core is 10~20
μm；The clad with a thickness of 5~20nm.
4. anode material for lithium-ion batteries according to claim 1, which is characterized in that the inside of the clad is conduction
Polymer；The outside of the clad is polyethylene glycol.
5. anode material for lithium-ion batteries according to claim 1, which is characterized in that the polyethylene glycol and conducting polymer
The mass ratio of object is 0.5~2:1.
6. the preparation method of any one of Claims 1 to 5 anode material for lithium-ion batteries, comprising the following steps:
(1) stoichiometrically the source Li, the source Mn and dopant are mixed, obtains mixed slurry；The dopant includes the source Mg, Zn
Source, the source Cu, the source Ni, the source Co, the source Cr, the source Al, the source Ga, the source In, the source Tl, the source Ti, the source Si or the source Zr；
The mixed slurry is successively dried, pre-burning and the processing of whole burning, obtains doping vario-property LiMn2O4；
(2) the doping vario-property LiMn2O4 that the step (1) obtains is refined, obtains nanoscale doping vario-property LiMn2O4；
(3) it pelletizes after mixing nanoscale doping vario-property LiMn2O4 and carbon nanotube that the step (2) obtains, obtains base
In the micron-size spherical core of carbon nanotube three-dimensional contact consolidation；
(4) disperse the core that conducting polymer monomer, dopant and step (3) are prepared in dehydrated alcohol, then plus
Enter oxidant, carries out oxidation polymerization, obtain intermediate product；
(5) it disperses the intermediate product that the step (4) obtains in polyglycol solution, obtains lithium-ion electric after removing solvent
Pond positive electrode.
7. preparation method according to claim 6, which is characterized in that in the step (1) temperature of pre-burning be 400~
450 DEG C, the time is 4~6h；The temperature burnt eventually is 750~825 DEG C, and the time is 12~18h.
8. preparation method according to claim 6, which is characterized in that the method pelletized in the step (3) is water base spray
Mist granulation, the environment temperature of the granulation are 120~200 DEG C.
9. preparation method according to claim 6, which is characterized in that dopant includes to toluene sulphur in the step (4)
One of sour sodium, dodecyl benzene sulfonic acid, camphorsulfonic acid, hydrochloric acid and dodecyl sodium sulfate are a variety of；The oxidant packet
Include one of ferric trichloride, ferric perchlorate, ammonium persulfate and hydrogen peroxide or a variety of；The temperature of the oxidation polymerization is 3~5
DEG C, the time is 5~10h.
10. preparation method according to claim 6, which is characterized in that the concentration of polyglycol solution in the step (5)
For 0.5~2mol/L.
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