CN108461730A - 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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- CN108461730A CN108461730A CN201810206972.4A CN201810206972A CN108461730A CN 108461730 A CN108461730 A CN 108461730A CN 201810206972 A CN201810206972 A CN 201810206972A CN 108461730 A CN108461730 A CN 108461730A
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Abstract
The present invention provides a kind of anode material for lithium-ion batteries and preparation method thereof, soluble lithium source, the sources A, the sources B are added into the dispersion liquid containing organic complexing agent, stir evenly acquisition solution, the pH for adjusting solution is 68, alcohol organic solvent is added into solution, it is stirred continuously until to form gel at 70 DEG C~90 DEG C, low-temperature sintering is first carried out after the ageing of gained gel, high temperature sintering is carried out after cooling again and obtains anode material for lithium-ion batteries, the molecular formula of gained anode material for lithium-ion batteries is LiAO2‑LixBOy(2≤x≤4,3≤y≤5).Anode material for lithium-ion batteries LiAO obtained by preparation method using the present invention2‑LixBOy(2≤x≤4,3≤y≤5) show high power capacity and good cycle performance.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof；Belong to lithium ion anode material and prepares neck
Domain.
Background technology
Demand with electric vehicle market to the lithium ion battery of high-energy-density is increasingly urgent to, lithium ion battery material conduct
The electrical source of power of electric vehicle was in past ten years, although its specific energy density has been improved at past 30 years very much,
It is still to also have further room for promotion.Rich lithium manganese oxide Li2MnO3And its derived material has shown high reversible appearance
Amount, the reason is that negatively charged oxonium ion is capable of providing charge compensation, and at the same time along with normal transient metal ion
Oxidation-reduction process, the unusual chemical property of this kind of materials show and new charge discharge mechanism, are novel height
Than one of the R＆D target of positive electrode of energy.
LiAO2-LixBOyPositive electrode ignores the orderly problem in transition metal sheath, can be regarded as consolidating for the two
Solution structure.Wherein LixBOyThe chemical property for introducing energy stabilizing material of component, enhances its circulation ability.
Multiphase solid solution structure mainly uses solid phase method to prepare at present, such as the Chinese invention of Publication No. CN104685679A
Patent, which discloses, a kind of preparing Li (Li0.233Mo0.467Cr0.3)O2The method of equal series materials, the material prepared have higher
Specific capacity, but cycle performance and high rate performance are to be improved.
Jinhyuk Lee (Energy Environ.Sci., 2015,8,3255) are prepared for three-phase solid solution using solid phase method
The cation disorder material Li of body1.2Ni1/3Ti1/3Mo2/15O2。Naoaki Yabuuchi(Chem.Commun., 2016,52,
2051) Li for using solid phase method to prepare1.3Nb0.3V0.4O2With good cycle performance, particle size is larger and uneven,
Reach 3 μm.
Solid phase method there are the problem of be that material needs multiple ball milling in preparation process, it is cumbersome to prepare materials process, week
Phase is long, and can not effectively control the appearance structure of material.
Ruiyong Chen (Phys.Chem.2016,18,7695) are prepared for Li using sol-gal process2FeVyTi1- yO4, a large amount of alkoxide has been used in raw material to increase the cost of production.And inorganic salts are selected to substitute alkoxide be effectively to reduce
Cost, while the influence needs of temperature and pH to material structure pattern are continued to optimize.
Invention content
In view of the deficiencies of the prior art, first purpose of the invention is intended to provide a kind of inexpensive, simple for process and controllable
The sol-gal process method for preparing anode material for lithium-ion batteries, gained lithium ion anode material uniform particle sizes, size are small, tool
There are excellent cycle performance and high rate performance.
Second object of the present invention is intended to provide a kind of anode material for lithium-ion batteries by obtained by above-mentioned preparation method.
To achieve the goals above, the following technical solutions are proposed by the present invention：
A kind of preparation method of anode material for lithium-ion batteries of the present invention, includes the following steps：By soluble lithium source, A
Source, the sources B are added into the dispersion liquid containing organic complexing agent, stir evenly acquisition solution, and the pH for adjusting solution is 6-8, to solution
Middle addition alcohol organic solvent is stirred continuously until to form gel at 70 DEG C~90 DEG C, first be carried out after the ageing of gained gel low
Temperature sintering carries out high temperature sintering after cooling and obtains anode material for lithium-ion batteries, gained anode material for lithium-ion batteries again
Molecular formula be LiAO2-LixBOy(2≤x≤4,3≤y≤5)；
The one kind of the A in V, Cr, Fe, Ni, Co, the one kind of the B in Nb, Mo, Ta, W；
The low-temperature sintering temperature is 450-600 DEG C, and sintering time is >=2h；
The temperature of the high temperature sintering is 850~1050 DEG C, and sintering time is 6h~for 24 hours.
The present invention is prepared anode material for lithium-ion batteries using sol-gal process, in forming gel process, respectively
It is to be uniformly mixed on a molecular scale between reactant so that finally formed reaction composition granule can be more uniform,
It is smaller.
Gained two-phase solid-solution material LiAO of the invention2-LixBOyIn (2≤x≤4,3≤y≤5), LiAO2It is electrochemistry
Active component, and LixBOyBoth the component as stabilizing material structure enhances circulation ability to stablize chemical property；Simultaneously again
It can be by coming from O in compound2-Part electron exchange contribute capacity, form new chemical reaction mechanism.
In the present invention, the dispersion liquid containing organic complexing agent refers to disperseing organic complexing agent in deionized water,
The dispersion liquid being mixing uniformly to form.
Preferred scheme, the one kind of the organic complexing agent in citric acid, polyvinylpyrrolidone.
Further preferred, the organic complexing agent is citric acid.
Preferred scheme, the one kind of the lithium source in lithium acetate, lithium hydroxide, lithium chloride, lithium nitrate；Described
One kind in acetate of the sources A selected from the A containing metal, chloride, nitrate, oxalates, ammonium salt, alkoxide；The sources B, which are selected from, to be contained
Acetate, chloride, nitrate, oxalates, the ammonium salt of metal B, one kind in alkoxide.
Further preferred, in the solution, the molar ratio of the sum of organic complexing agent and metallic element (Li+A+B) is 1:1
~2.As a further preference, in the solution, the molar ratio of organic complexing agent and (Li+A+B) are 1:1~1.5.
Preferred scheme, in the dispersion liquid, Li elements：Element A：The molar ratio of B element is 1.2~2.5:0.4~
0.6:0.4~0.6.
Preferred scheme, the one kind of the A in V, Cr；The one kind of the B in Nb, Ti.Described preferred
In scheme, it is formed by two-phase solid-solution material LiAO2-LixBOyIn (2≤x≤4,3≤y≤5), LiAO2Group be divided into
LiCrO2、LiVO2In one kind, LixBOyThe group of (2≤x≤4,3≤y≤5) is divided into Li3NbO5、Li2TiO3In one kind.
Preferred scheme, when A is selected from V, and B is selected from Nb, carbon source is added together with soluble lithium source, the sources A, the sources B to
In dispersion liquid containing organic complexing agent.
Further preferably the carbon source is selected from sucrose, glucose, one kind in PVA.
Inventor has found, when A is selected from V, and B is selected from Nb, after carbon source is added, the material finally obtained is with more excellent
Performance.
It is further preferably, the addition of the carbon source according to the molar ratio, carbon：Elemental lithium is 2~4:1.
Preferred scheme stirs evenly acquisition solution, and the pH for adjusting solution is 7-8, and it is organic molten that alcohols is added into solution
Agent is stirred continuously until to form gel at 80 DEG C~90 DEG C.
Inventor is the study found that mixing speed has a certain impact to material property tool, preferably, described stir evenly
Mixing speed when obtaining solution is 300~600r/min；Mixing time is 60~180min；
Mixing speed when being stirred continuously until to form gel is 300~600r/min；Mixing time be 90~
180min。
As a further preference, the mixing speed stirred evenly when obtaining solution is 400~600r/min；Stirring
Time is 60~120min；
Mixing speed when being stirred continuously until to form gel is 400~600r/min；Mixing time be 90~
120min。
Preferred scheme, the alcohol organic solvent are selected from least one of ethyl alcohol, ethylene glycol, methanol, isopropanol.Make
To be preferred, the alcohol organic solvent is ethylene glycol.
Inventor has found in an experiment, and second is added after being added using citric acid as organic complexing agent in sol-gel process
Glycol, final resulting materials can obtain more excellent performance.
Preferred scheme, the addition of the alcohol organic solvent according to the molar ratio, alcohol organic solvent：Metallic element it
(Li+A+B)=4:1~5:1.The addition of the alcohol organic solvent according to the molar ratio, alcohol organic solvent：(Li+A+B)
=4:1~4.5:1.
The time of preferred scheme, the gel ageing is 8h~10h.
Preferred scheme, after gel ageing, processing is dried in first gel, then carries out low-temperature sintering.
Preferred scheme, the low-temperature sintering temperature are 450-500 DEG C, and sintering time is 2h~4h.
Preferred scheme, it is cooling after gained low-temperature sintering product, first carry out tabletting and carry out high temperature sintering again, when the tabletting
Pressure be 6~8MPa.
The temperature of preferred scheme, the high temperature sintering is 850-1050 DEG C, sintering time 10h-24h.
As a further preference, when A is selected from Cr, and B is selected from Nb, the temperature of the high temperature sintering is 900-950 DEG C；
The high temperature sintering time is 8~14h；
When A is selected from V, and B is selected from Nb, the temperature of the high temperature sintering is 950-1000 DEG C；The high temperature sintering time be 12~
24h；
When A is selected from V, and B is selected from Ti, the temperature of the high temperature sintering is 950-1000 DEG C；The high temperature sintering time is
12~20h；
The atmosphere of preferred scheme, the low-temperature sintering and high temperature sintering is inert atmosphere.
As a further preference, the low-temperature sintering and the atmosphere of high temperature sintering are argon gas atmosphere or nitrogen atmosphere.
Preferred scheme, the A are Cr；The B is Nb；The molecular formula of gained anode material for lithium-ion batteries is
LiCrO2-Li3NbO4；It recycles the specific capacity of 30 circles and is more than first circle specific capacity.
The present invention also unexpected discovery, when A is selected from Cr；When the B is selected from Nb, gained two-phase solid-solution material
LiCrO2-Li3NbO4Specific capacity does not reduce and rises instead in cyclic process, shows dilatation ability.
A kind of anode material for lithium-ion batteries by obtained by above-mentioned preparation method, point of the anode material for lithium-ion batteries
Minor is LiCrO2-Li3NbO4, wherein Cr：The atomic ratio of Nb is 0.4~0.6:0.4~0.6.
The principle of the present invention and advantage：
Gained two-phase solid-solution material LiAO of the invention2-LixBOyIn (2≤x≤4,3≤y≤5), LiAO2It is electrochemistry
Active component, LixBOyComponent as stabilizing material structure introduces, and improves material safety and structural stability, simultaneously
LixBOyIt can be by coming from O in compound2-Electron exchange, form new chemical reaction mechanism.
The present invention uses two-phase solid-solution material LiAO prepared by sol-gal process2-LixBOy(2≤x≤4,3≤y≤
5), due to being to be uniformly mixed on a molecular scale in forming gel process, between each reactant so that finally formed
Reacting composition granule can be more uniformly smaller, is conducive to the performance for promoting further material.
Inventor's also unexpected discovery in an experiment, when A is selected from Cr；When the B is selected from Nb, gained two-phase solid solution
Material LiCrO2-Li3NbO4Specific capacity does not reduce and rises instead in cyclic process, shows dilatation ability.
Present invention process process is simple, easily controllable, the two-phase solid-solution material LiAO of gained2-LixBOy
(2≤x≤4,3≤y≤5) specific capacity is high, cycle performance is excellent！
Description of the drawings
Fig. 1 is the 0.57LiCrO that embodiment 1 and comparative example 1 obtain2-0.43Li3NbO4SEM figure；Wherein, Fig. 1 (a) is
1 gained 0.57LiCrO of embodiment2-0.43Li3NbO4SEM figure；Fig. 1 (b) is 1 gained 0.57LiCrO of comparative example2-
0.43Li3NbO4SEM figure.
Fig. 2 is the 0.57LiVO that embodiment 3 and comparative example 2 obtain2-0.43Li3NbO44SEM figure；Wherein Fig. 2 (a) is
3 gained 0.57LiVO of embodiment2-0.43Li3NbO44SEM figure；
Fig. 2 (b) is 2 gained 0.57LiVO of comparative example2-0.43Li3NbO44SEM figure.
Fig. 3 is the 0.57LiCrO that embodiment 1 and comparative example 1 obtain2-0.43Li3NbO4Material is in 20mA/g current densities
Under, the cyclic curve figure in 50 DEG C and 1.5V~4.8V voltage ranges.
Fig. 4 is the 0.57LiVO that embodiment 3 and 2 two methods of comparative example obtain2-0.43Li3NbO44Material is in 20mA/g
Cyclic curve figure under current density, in 50 DEG C and 1.5V~4.8V voltage ranges.
Specific implementation method
Embodiment 1
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates are stirred continuously under 600r/min mixing speeds, and it is uniform that stirring 60min to raw material is completely dissolved acquisition
After solution, it is 7.0 to adjust pH, and it (is about 4 with metal ion molar ratio that ethylene glycol 4.5ml, which is added,：1), at 80 DEG C stirring until going out
Existing gel (mixing speed 500r/min)；Mixing time is 100min；
Gained gel is aged 8h；After be dried and low-temperature sintering (2h at 500 DEG C) in a nitrogen atmosphere.By gained low temperature
Sintered product, after cooling under the pressure of 6Mpa, tabletting is in a nitrogen atmosphere in 950 DEG C of heat preservation sintering 14h at sequin
Obtain anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Shape measure is carried out to prepared material using scanning electron microscope, wherein Fig. 1 (a) is prepared for sol-gal process
0.57LiCrO2-0.43Li3NbO4Material, it can be seen that 800nm-1 μm of collosol and gel resulting materials particle size from Fig. 1 (a)
Between.
Fig. 3 is the 0.57LiCrO that embodiment 1 obtains2-0.43Li3NbO4Material under 20mA/g current densities, 50 DEG C and
Cyclic curve figure in 1.5V~4.8V voltage ranges.It can be seen from the figure that first circle specific capacity reaches 172mAh/g, cycle 30
Circle capacity has reached 195mAh/g, and the specific capacity of 30 circle of cycle is more than first circle specific capacity, illustrates 0.57LiCrO2-
0.43Li3NbO4Material has further dilatation ability under the activation of electric current.
Embodiment 2
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by citric acid:1.5) exist
Ionized water is uniformly dispersed, and obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates are stirred continuously under 400r/min mixing speeds, and it is uniform that stirring 120min to raw material is completely dissolved acquisition
After solution, pH8.0 is adjusted, it (is 4.5 with metal ion molar ratio that ethylene glycol 5ml, which is added,：1), at 80 DEG C stirring until coagulating
Glue (mixing speed 400r/min)；Mixing time is 120 min；
After gained gel is aged 10h；It is dried, then carries out low-temperature sintering (4h at 450 DEG C) under an argon atmosphere.It will
Gained low-temperature sintering product, it is cooling after under the pressure of 7Mpa, tabletting at 1mm thickness sequin (0.01mol) and in argon gas gas
The lower 900 DEG C of heat preservation sintering 8h of atmosphere obtain anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Under 20mA/g current densities, the material of 50 DEG C and the gained to embodiment 2 in 1.5V~4.8V voltage ranges
Carry out the test of cycle performance.Its first circle specific capacity reaches 168.2mAh/g, and 30 circle capacity of cycle has reached 192.8mAh/g,
The specific capacity of 30 circle of cycle is more than first circle specific capacity, illustrates 0.57LiCrO2-0.43Li3NbO4Material has under the activation of electric current
There is further dilatation ability.
Embodiment 3
Sol-gal process prepares 0.57LiVO2-0.43Li3NbO4Material：0.01 by citric acid (with metal ion molar ratio
It is 1:2) it is uniformly dispersed in ionized water, obtains dispersion liquid；0.013mol lithium acetates, 0.004mol metavanadic acids are added into dispersion liquid
Ammonia, 0.003mol niobium oxalates, are stirred continuously under 300r/min mixing speeds, and it is equal that stirring 180min to raw material is completely dissolved acquisition
After one solution, pH8 is adjusted, 1g sucrose is added, it (is about 5 with metal ion molar ratio to add ethylene glycol 5.6ml：1), 80 DEG C
Lower stirring is until there is gel (mixing speed 600r/min)；Mixing time is 90min；
Gained gel is aged 8h；After be dried, then low-temperature sintering (2h at 500 DEG C) in a nitrogen atmosphere.Gained is low
After warm sintered product cooling under the pressure of 7.5Mpa, tabletting is at thick sequin, then at the lower 950 DEG C of heat preservation sinterings of argon gas atmosphere
Final material is synthesized for 24 hours.
Using scanning electron microscope to carrying out Shape measure to prepared material, wherein Fig. 2 (a) is prepared by embodiment 3
0.57LiVO2-0.43Li3NbO4Material, it can be seen that resulting materials average-size is 200nm from Fig. 2 (a), and particle is equal
It is even.
Fig. 4 is the 0.57LiVO that embodiment 3 obtains2-0.43Li3NbO4Material under 20mA/g current densities, 50 DEG C and
Cyclic curve figure in 1.5V~4.8V voltage ranges.It can be seen from the figure that first circle specific capacity reaches 179mAh/g, cycle 30
Circle capacity has reached 157.9mAh/g.
Embodiment 4
Sol-gal process prepares 0.5LiVO2-0.5Li2TiO3Citric acid (is 1 with metal ion molar ratio by material:1)
It is uniformly dispersed in ethanol, obtains dispersion liquid；0.012mol lithium acetates, 0.004mol metavanadic acid ammonia are added into dispersion liquid,
1.4380ml (0.004mol) butyl titanate, is stirred continuously under 500r/min mixing speeds, and stirring 90min is complete to raw material
After dissolving obtains uniform solution, pH8 is adjusted, it (is 4 with metal ion molar ratio that ethylene glycol, which is added,：1), at 80 DEG C stirring until
There is gel (mixing speed 300r/min)；Mixing time is 180min；
Gained gel is aged 10h；After be dried, then in a nitrogen atmosphere carry out low-temperature sintering (2h at 500 DEG C).Institute
After obtaining the cooling of low-temperature sintering product, under the pressure of 8Mpa, tabletting is kept the temperature in 1000 DEG C in a nitrogen atmosphere at sequin
20h synthesizes final material.
Electrochemical property test is carried out to above-mentioned material, resulting materials are under 20mA/g current densities, and discharge specific volume for the first time
Amount be 135.4mAh/g, cycle 30 circle after, specific discharge capacity be 113.6mAh/g.
Comparative example 1
Common solid phase method prepares 0.57LiCrO2-0.43Li3NbO44Material：According to 0.57LiCrO2-0.43Li3NbO4Point
The metering ratio of minor, by Nb2O5、Li2CO3、Cr2O3, it is dry with ball grinder with 300r/m speed ball milling 10h, after first carry out low temperature
It is sintered (2h at 500 DEG C).Then after at 950 DEG C, heat preservation synthesizes final material tabletting for 24 hours, 950 DEG C of heat preservations for 24 hours, obtain target material
Material.
Shape measure is carried out to prepared material using scanning electron microscope, if Fig. 1 (b) is 1 common solid phase legal system of comparative example
Standby 0.57LiCrO2-0.43Li3NbO4Material, it can be seen that material granule made from solid phase method is reunited seriously from Fig. 1 (b).
Fig. 3 is the 0.57LiCrO that embodiment 1 obtains2-0.43Li3NbO4Material, under 20mA/g current densities, 50 DEG C and
Cyclic curve figure in 1.5V~4.8V voltage ranges.
It can be seen from the figure that the common solid phase methods of Fig. 3 prepare 0.57LiCrO2-0.43Li3NbO4Material, can be with from figure
Find out, capacity only has 161mAh/g, and after 30 circle cycles, capacity decays to rapidly 54mAh/g.
Comparative example 2
Common solid phase method prepares 0.57LiVO2-0.43Li3NbO4Material：According to 0.57LiVO2-0.43Li3NbO4Molecular formula
Metering ratio, by Nb2O5、Li2CO3、V2O5, sucrose, with ball grinder with 300r/m speed ball milling 10h, it is dry after low-temperature sintering
After (2h at 500 DEG C) tabletting, 950 DEG C of heat preservations for 24 hours, obtain target material.
Shape measure is carried out to prepared material using scanning electron microscope, wherein Fig. 2 (b) is 2 common solid phase method of comparative example
Prepare 0.57LiVO2-0.43Li3NbO4Material, from Fig. 2 (b) it can be seen that resulting materials granular size it is uneven, grain size compared with
Greatly.
Fig. 4 is that 2 common solid phase method of comparative example prepares 0.57LiVO2-0.43Li3NbO4Material is in 20mA/g current densities
Under, the cyclic curve figure in 50 DEG C and 1.5V~4.8V voltage ranges., it can be seen from the figure that capacity only has 163.3mAh/g,
After 30 circle cycles, capacity decays to rapidly 122mAh/g.
Comparative example 3
0.33LiCrO2-0.67Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by citric acid:1.5) exist
Ionized water is uniformly dispersed, and obtains dispersion liquid；Into dispersion liquid be added molecular formula stoichiometric ratio lithium nitrate (0.0234mol),
Cadmium nitrate (0.0033mol), niobium oxalate (0.0067mol), are stirred continuously under 400r/min mixing speeds, and stirring 120min is extremely
After raw material is completely dissolved acquisition uniform solution, pH7 is adjusted, it (is 4 with metal ion molar ratio that ethylene glycol, which is added,：1) it, stirs at 80 DEG C
It mixes until there is gel (mixing speed 400r/min)；Mixing time is 120min；
After gained gel is aged 10h；It is dried, then carries out low-temperature sintering (4h at 450 DEG C) under an argon atmosphere.It will
Gained low-temperature sintering product, after cooling under the pressure of 6Mpa, tabletting is at sequin and in the lower 950 DEG C of heat preservation sinterings of argon gas atmosphere
30h obtains anode material for lithium-ion batteries 0.33LiCrO2-0.67Li3NbO4。
The material to 3 gained of comparative example under 20mA/g current densities, in 50 DEG C and 1.5V~4.8V voltage ranges into
The test of row cycle performance.Its first circle specific capacity reaches 118.2mAh/g, and 30 circle capacity of cycle has reached 80.8mAh/g.
Comparative example 4
0.75LiCrO2-0.25Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by citric acid:1.5) exist
Ionized water is uniformly dispersed, and obtains dispersion liquid；Lithium nitrate (0.015mol, the cadmium nitrate for calculating gained ratio are added into dispersion liquid
(0.0075mol), niobium oxalate (0.0025mol), is stirred continuously under 400r/min mixing speeds, and stirring 120min is complete to raw material
After fully dissolved obtains uniform solution, pH7 is adjusted, it (is 4 with metal ion molar ratio that ethylene glycol, which is added,：1), at 80 DEG C stirring until
There is gel (mixing speed 400r/min)；Mixing time is 120min；
After gained gel is aged 10h；It is dried, then carries out low-temperature sintering (4h at 450 DEG C) under an argon atmosphere.It will
Gained low-temperature sintering product, after cooling under the pressure of 6Mpa, tabletting is at sequin) and burnt in the lower 950 DEG C of heat preservations of argon gas atmosphere
It ties 12h and obtains anode material for lithium-ion batteries 0.75LiCrO2-0.25Li3NbO4。
Under 20mA/g current densities, the material of the gained of 50 DEG C and the comparative example 4 in 1.5V~4.8V voltage ranges into
The test of row cycle performance.Its first circle specific capacity reaches 160.2mAh/g, and 30 circle capacity of cycle has reached 50.3mAh/g.
Comparative example 5
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates are stirred continuously under 600r/min mixing speeds, and it is uniform that stirring 60min to raw material is completely dissolved acquisition
After solution, it is 7.0 to adjust pH, and it (is about 4 with metal ion molar ratio that ethylene glycol 4.5ml, which is added,：1), at 80 DEG C stirring until going out
Existing gel (mixing speed 500r/min)；Mixing time is 100min；
Gained gel is aged 8h；After be dried and low-temperature sintering (2h at 500 DEG C) in a nitrogen atmosphere.By gained low temperature
Sintered product, after cooling under the pressure of 6Mpa, tabletting is in a nitrogen atmosphere in 900 DEG C of heat preservation sintering 28h at sequin
Obtain anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Gained 0.57LiCrO2-0.43Li3NbO4Material, specific capacity only have 161mAh/g, after 30 circle cycles, specific volume
Amount decays to 84.5mAh/g rapidly.
Comparative example 6
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates, and be stirred continuously, after being completely dissolved, pH7.0 is adjusted, ethylene glycol 4.5ml is added (with metal ion mole
Than being 4：1), at 80 DEG C stirring until there is gel (mixing speed 500r/min)；
After being dried after the ageing of gained gel under the pressure of 5Mpa, it is pressed into sequin, 12h is kept the temperature at 950 DEG C is
Obtain anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Under 20mA/g current densities, the material of 50 DEG C and the gained to embodiment 2 in 1.5V~4.8V voltage ranges
Carry out the test of cycle performance.Its first circle specific capacity is 142.2mAh/g, and 30 circle capacity of cycle is 112.1mAh/g.
Inventor has found that, without low-temperature sintering, material expand is serious after carrying out high temperature sintering, causes test performance not
It is good.
Comparative example 7
Prepare 0.57LiCrO2-0.43Li3NbO4Remaining condition of material is same as Example 3, is only added without sucrose, first circle
Specific capacity can only achieve 142mAh/g.
Comparative example 8
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates, and be stirred continuously, after being completely dissolved, it is 5 to adjust pH, and ethylene glycol 4.5ml is added (with metal ion mole
Than being 4：1) it, stirs at 80 DEG C.
Gained gel ageing after be dried after under the pressure of 5Mpa, tabletting at 2mm thickness sequin (0.01mol)
950 DEG C of heat preservation 12h obtain anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Under 20mA/g current densities, the material of 50 DEG C and the gained to comparative example 8 in 1.5V~4.8V voltage ranges
Carry out the test of cycle performance.First circle specific capacity only reaches 161.1mAh/g.
Comparative example 9
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates, and be stirred continuously, after being completely dissolved, it is 9 to adjust pH, and ethylene glycol 4.5ml is added (with metal ion mole
Than being 4：1) it, stirs at 80 DEG C.
Gained gel ageing after be dried after under the pressure of 5Mpa, tabletting at 1mm thickness sequin (0.01mol)
950 DEG C of heat preservation 12h obtain anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Under 20mA/g current densities, the material of 50 DEG C and the gained to comparative example 9 in 1.5V~4.8V voltage ranges
Carry out the test of cycle performance.Its first circle specific capacity is 149.2mAh/g, and 30 circle capacity of cycle is 100.5mAh/g.
Comparative example 10
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates are stirred continuously under 600r/min mixing speeds, and it is uniform that stirring 60min to raw material is completely dissolved acquisition
After solution, it is 7.0 to adjust pH, and it (is 4 with metal ion molar ratio that ethylene glycol 4.5ml, which is added,：1), at 60 DEG C stirring until occurring
Gel (mixing speed 500r/min)；Mixing time reaches 12h；
Gained gel is aged 8h；After be dried and low-temperature sintering (2h at 500 DEG C) in a nitrogen atmosphere.By gained low temperature
Sintered product, after cooling under the pressure of 6Mpa, tabletting is at the sequin (0.01mol) of 1mm thickness in a nitrogen atmosphere in 950
DEG C heat preservation sintering 12h obtains anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
Under 20mA/g current densities, the material of 50 DEG C and the gained to comparative example 10 in 1.5V~4.8V voltage ranges
Carry out the test of cycle performance.Its first circle specific capacity is 161.2mAh/g, and 30 circle capacity of cycle is 145.9mAh/g.
Comparative example 11
0.57LiCrO2-0.43Li3NbO4The preparation of material：(it is 1 with metal ion molar ratio by 0.02mol citric acids:
1) it is uniformly dispersed in ionized water, obtains dispersion liquid；Be added into dispersion liquid 0.013mol lithium nitrates, 0.004mol cadmium nitrates,
0.003mol niobium oxalates are stirred continuously under 600r/min mixing speeds, and it is uniform that stirring 60min to raw material is completely dissolved acquisition
After solution, it is to be stirred at 7.0,80 DEG C until there is gel (mixing speed 500r/min) to adjust pH；Mixing time is
100min；
Gained gel is aged 8h；After be dried and low-temperature sintering (2h at 500 DEG C) in a nitrogen atmosphere.By gained low temperature
Sintered product, after cooling under the pressure of 6Mpa, tabletting is at the sequin (0.01mol) of 1mm thickness in a nitrogen atmosphere in 950
DEG C heat preservation sintering 12h obtains anode material for lithium-ion batteries 0.57LiCrO2-0.43Li3NbO4。
The material to 11 gained of comparative example under 20mA/g current densities, in 50 DEG C and 1.5V~4.8V voltage ranges into
The test of row cycle performance.Its first circle specific capacity is 146mAh/g, and 30 circle capacity of cycle is 97.9mAh/g.
Claims (10)
1. a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that：Include the following steps：By soluble lithium
Source, the sources A, the sources B are added into the dispersion liquid containing organic complexing agent, stir evenly acquisition solution, and the pH for adjusting solution is 6-8, to
Alcohol organic solvent is added in solution, is stirred continuously until to form gel at 70 DEG C~90 DEG C, it is advanced after the ageing of gained gel
Row low-temperature sintering carries out high temperature sintering after cooling and obtains anode material for lithium-ion batteries, gained lithium ion cell positive again
The molecular formula of material is LiAO2-LixBOy(2≤x≤4,3≤y≤5)；
The one kind of the A in V, Cr, Fe, Ni, Co, the one kind of the B in Nb, Mo, Ta, W；
The low-temperature sintering temperature is 450-600 DEG C, and sintering time is >=2h；
The temperature of the high temperature sintering is 850~1050 DEG C, and sintering time is 6h~for 24 hours.
2. a kind of preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：It is described organic
The one kind of complexing agent in citric acid, polyvinylpyrrolidone；
The one kind of the lithium source in lithium acetate, lithium hydroxide, lithium chloride, lithium nitrate；The sources A are selected from A containing metal
Acetate, chloride, nitrate, oxalates, ammonium salt, one kind in alkoxide；The sources B be selected from the B containing metal acetate,
Chloride, nitrate, oxalates, ammonium salt, one kind in alkoxide；
In the solution, the molar ratio of organic complexing agent and (Li+A+B) are 1:1~2；
The alcohol organic solvent is selected from least one of ethyl alcohol, ethylene glycol, methanol, isopropanol；
The addition of the alcohol organic solvent according to the molar ratio, alcohol organic solvent：(Li+A+B)=4:1~5:1.
In the dispersion liquid, Li elements：Element A：The molar ratio of B element is 1.2~2.5:0.4~0.6:0.4~0.6.
3. a kind of preparation method of anode material for lithium-ion batteries according to claim 2, it is characterised in that：
The organic complexing agent is citric acid, and the alcohol organic solvent is ethylene glycol；
In the solution, the molar ratio of organic complexing agent and (Li+A+B) are 1:1~1.5.
The addition of the alcohol organic solvent according to the molar ratio, alcohol organic solvent：(Li+A+B)=4:1~4.5:1.
4. a kind of preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：
Acquisition solution is stirred evenly, the pH for adjusting solution is 7-8, alcohol organic solvent is added into solution, at 80 DEG C~90 DEG C
Under be stirred continuously until to form gel,
The mixing speed stirred evenly when obtaining solution is 300~600r/min；Mixing time is 60~180min；
Mixing speed when being stirred continuously until to form gel is 300~600r/min；Mixing time is 90~180min.
The time of the gel ageing is 8h~10h.
5. a kind of preparation method of anode material for lithium-ion batteries according to claim 4, it is characterised in that：
The mixing speed stirred evenly when obtaining solution is 400~600r/min；Mixing time is 60~120min；
Mixing speed when being stirred continuously until to form gel is 400~600r/min；Mixing time is 90~120min.
6. a kind of preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The A choosings
From one kind in V, Cr；The one kind of the B in Nb, Ti.
7. a kind of preparation method of anode material for lithium-ion batteries according to claim 6, it is characterised in that：
The low-temperature sintering temperature is 450~500 DEG C, and the low sintering time is 2h~4h；
When A is selected from Cr, and B is selected from Nb, the temperature of the high temperature sintering is 900-950 DEG C；
The high temperature sintering time is 8~14h；
When A is selected from V, and B is selected from Nb, the temperature of the high temperature sintering is 950-1000 DEG C；
The high temperature sintering time be 12~for 24 hours；
When A is selected from V, and B is selected from Ti, the temperature of the high temperature sintering is 950-1000 DEG C；
The high temperature sintering time is 12~20h.
8. a kind of preparation method of anode material for lithium-ion batteries according to claim 6, it is characterised in that：
When A is selected from V, and B is selected from Nb, carbon source is added together with soluble lithium source, the sources A, the sources B to point containing organic complexing agent
In dispersion liquid, the carbon source is selected from sucrose, glucose, one kind in PVA；The addition of the carbon source according to the molar ratio, carbon：
Elemental lithium is 2~4:1.
9. a kind of preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The A is
Cr；The B is Nb；The molecular formula of gained anode material for lithium-ion batteries is LiCrO2-Li3NbO4；It recycles the specific capacity of 30 circles
More than first circle specific capacity.
10. according to the anode material for lithium-ion batteries prepared by any one of claim 1-9 claims, it is characterised in that：Institute
The molecular formula for stating anode material for lithium-ion batteries is LiCrO2-Li3NbO4, wherein Cr：The atomic ratio of Nb is 0.4~0.6:0.4~
0.6。
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