CN105280895B - A kind of composite cathode material of lithium ion battery and preparation method thereof - Google Patents

A kind of composite cathode material of lithium ion battery and preparation method thereof Download PDF

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CN105280895B
CN105280895B CN201510578783.6A CN201510578783A CN105280895B CN 105280895 B CN105280895 B CN 105280895B CN 201510578783 A CN201510578783 A CN 201510578783A CN 105280895 B CN105280895 B CN 105280895B
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lithium
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lithium ion
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CN105280895A (en
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马守龙
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a kind of composite cathode material of lithium ion battery and preparation method thereof, and the lithium-ion negative pole composite is according to chemical formula xLi3VO4·(1‑x)Li4Ti5O12(wherein 0.5≤x≤1) stoichiometric proportion is combined；Its preparation method is：Lithium source and vanadium source are weighed, " additive and solvent " or " complexing agent and solvent " is added and forms solution or slurry A afterwards；Lithium source and titanium source are weighed, " additive and solvent " or " complexing agent and solvent " is added and forms solution or slurry B afterwards；After A and B is well mixed by the method for liquid phase or solid phase, dry, sintering obtains Li3VO4And Li4Ti5O12Two-phase composite material.The composite that the present invention is obtained takes full advantage of lithium vanadate as lithium ion battery negative material has the characteristic of suitable embedded abjection current potential and considerable volume, thus with higher coulombic efficiency, higher specific capacity and good high rate performance.

Description

A kind of composite cathode material of lithium ion battery and preparation method thereof
Technical field
The invention belongs to lithium battery material field, and in particular to a kind of Li3VO4And Li4Ti5O12The compound lithium ion of two-phase Cell negative electrode material and preparation method thereof.
Background technology
At present, graphite because its have higher stability and cost performance be widely used in lithium ion battery cathode material In, its theoretical capacity is 372mAh/g, belongs to embedded abjection type ion cathode material lithium.But in charge and discharge process, graphite Intercalation potential is less than 0.1V (vs Li/Li+), cause to be likely to occur Li dendrite in cyclic process and pierce through barrier film and cause battery short Road, so as to cause the potential safety hazard of power vehicle.In order to eliminate the appearance of such a phenomenon, researchers are looked for by effort for many years To the negative material that a kind of discharge platform is suitable, capacity and graphite-phase are worked as.Japanese Scientists find lithium vanadate (Li within 20133VO4) Negative material, its discharge potential is 0.5~1V (vs Li/Li+), compared to graphite there is higher discharge potential to improve The security performance of battery, and there is higher capacity, battery when being matched with other positive electrodes relative to lithium titanate anode material With broader discharge voltage, so that battery has higher capacity.
Research discovery, lithium vanadate (Li3VO4) belong to ion conductor, with very high ionic conductivity, but its electronic conduction The very poor intimate insulator of property so that its chemical property is severely impacted, especially its cycle performance.It is conductive in order to improve it Property, researchers start to carry out lithium vanadate particle nanosizing and surface modification treatment, and most conventional methods are exactly to introduce carbon materials Material improves its electric conductivity, (the J.Power Sources 2014,252 such as Liang:Carbon bag 244-247) has been carried out to lithium vanadate Cover, and (NanoLett., 2013,13 (10) such as Shi:4715-4720) it is combined using lithium vanadate with graphene film, to lithium vanadate Cycle performance improves and obtains preferable result.But can be formed on electrode and electrolyte face after passing through carbon material processing With traditional carbon material formed solid electrolyte interface film (SEI), still can cause bad to the security performance of battery Influence.
The content of the invention
One of the object of the invention is to improve the cycle performance and security performance of material by not introducing carbon material, to meet Requirement of the following electric automobile industry to electrokinetic cell long-life high safety performance；The two of the object of the invention are by changing vanadic acid The ratio of lithium and lithium titanate is tried one's best while circulating effect is improved and improves appearance of the negative material when other positive electrodes are matched Amount, so as to improve battery durable ability.
In order to reach object above, the present invention intends being achieved using following technical scheme.
A kind of composite cathode material of lithium ion battery, by Li3VO4And Li4Ti5O12Two-phase is according to chemical formula xLi3VO4·(1- x)Li4Ti5O12It is combined, wherein 0.5≤x≤1.
Preferably, the preparation method of described composite cathode material of lithium ion battery, comprises the following steps：
(1) according to mol ratio Li：V=3.0~3.2:1 weighs lithium source and vanadium source, adds " additive and solvent " or " network Mixture and solvent " forms solution or slurry A afterwards；
(2) according to mol ratio Li：Ti=4.0~4.1:5 weigh lithium source and titanium source, add " additive and solvent " or " complexing agent and solvent " forms solution or slurry B afterwards；
(3) after A and B is well mixed by the method for liquid phase or solid phase, it is warming up to 70-90 DEG C of evaporation solvent and forms wet Air dry oven is transferred to after gel 12~48h is dried under the conditions of 80-120 DEG C, obtain Li3VO4And Li4Ti5O12Presoma；
(4) (3) are prepared into presoma in Muffle furnace in, with stove Temperature fall, being taken after 400-500 DEG C of pre-burning 3-5h Go out sample by grinding after 600~900 DEG C, 6~12h of sintering obtains Li3VO4And Li4Ti5O12The compound lithium-ion electric of two-phase Pond negative material.
Preferably, the lithium source is one or both of lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate；Vanadium source is inclined One kind in ammonium vanadate or vanadic anhydride；Titanium source be butyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium dioxide, One or both of titanium tetrachloride.
Preferably, mixed in the step (3) using the method for solid phase, additive during synthetic composite material is to help Grinding agent；The grinding aid is in polymerized polyalcohol, polyalcohol amine, triethanolamine, triisopropanolamine, ethylene glycol, diethylene glycol It is one or two kinds of.
Preferably, mixed in the step (3) using the method for liquid phase, the complexing agent of synthetic composite material is organic Acid；The organic acid is one or more of groups in citric acid, glycine, salicylic acid, oxalic acid, adipic acid, ethylenediamine tetra-acetic acid Close.
Preferably, the solvent is deionized water, ethanol, ethylene glycol, the one or two of acetone.
Preferably, the sintering atmosphere is air.
The beneficial effects of the present invention are：
(1)Li3VO4And Li4Ti5O12All be to contain lithium titanate cathode material, both into phase temperature close, therefore handle can be passed through Lithium source is added after vanadium source is well mixed with titanium source the perfect two-phase composite material of crystallization is thermally treated resulting in using mutually synthermal progress；
(2) lithium vanadate and the composite of lithium titanate obtained by the present invention, which is used as lithium ion battery negative material, to be had Higher coulombic efficiency, higher specific capacity and good high rate performance, taking full advantage of lithium vanadate has suitable embedded abjection The characteristic of current potential and considerable volume, is expected to be widely popularized and applied in electrokinetic cell industry.
Brief description of the drawings
Fig. 1 is the synthesis x of embodiment 1 Li3VO4·(1-x)Li4Ti5O12The XRD spectrum of composite；
Fig. 2 is the synthesis x of embodiment 1 Li3VO4·(1-x)Li4Ti5O12The SEM spectrum of composite；
Fig. 3 is the synthesis x of embodiment 1 Li3VO4·(1-x)Li4Ti5O12The charging and discharging curve figure of composite；
Fig. 4 is the synthesis x of embodiment 1 Li3VO4·(1-x)Li4Ti5O12The cyclic curve figure of composite.
Embodiment
In order to which preferably the present invention will be described in detail, circulated the following is lithium vanadate lithium ion battery negative material is improved The method specific experiment process of performance, embodiment is illustrated using liquid phase method, but the present invention is not limited to this.
Embodiment 1
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 12.61g is weighed as x=0.75 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.51g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.365g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.75, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 17.36g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 13.45g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 120 DEG C of air dry ovens drying 24h, obtain 0.75Li3VO4·0.25Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 800 DEG C of sintering 10h after grinding and obtains 0.75Li3VO4·0.25Li4Ti5O12Lithium ion battery is born Pole composite.
Embodiment 2
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 12.61g is weighed as x=0.75 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.51g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.365g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.75, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 17.36g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 13.45g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 120 DEG C of air dry ovens drying 24h, obtain 0.75Li3VO4·0.25Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 700 DEG C of sintering 10h after grinding and obtains 0.75Li3VO4·0.25Li4Ti5O12Lithium ion battery is born Pole composite.
Embodiment 3
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 12.61g is weighed as x=0.75 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.51g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.365g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.75, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 17.36g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 13.45g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 80 DEG C of air dry ovens drying 12h, obtain 0.75Li3VO4·0.25Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 900 DEG C of sintering 10h after grinding and obtains 0.75Li3VO4·0.25Li4Ti5O12Lithium ion battery is born Pole composite.
Embodiment 4
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 12.61g is weighed as x=0.75 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.51g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.365g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.75, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 17.36g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 13.45g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 120 DEG C of air dry ovens drying 24h, obtain 0.75Li3VO4·0.25Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 800 DEG C of sintering 8h after grinding and obtains 0.75Li3VO4·0.25Li4Ti5O12Negative electrode of lithium ion battery Composite.
Embodiment 5
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 12.61g is weighed as x=0.75 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.51g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.365g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.75, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 17.36g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 13.45g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 100 DEG C of air dry ovens drying 24h, obtain 0.75Li3VO4·0.25Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 700 DEG C of sintering 12h after grinding and obtains 0.75Li3VO4·0.25Li4Ti5O12Lithium ion battery is born Pole composite.
Embodiment 6
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 13.45g is weighed as x=0.8 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.73g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.99g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.8, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 13.89g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 10.76g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 120 DEG C of air dry ovens drying 24h, obtain 0.8Li3VO4·0.2Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 800 DEG C of sintering 10h after grinding and obtains 0.8Li3VO4·0.2Li4Ti5O12Negative electrode of lithium ion battery Composite.
Embodiment 7
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 13.45g is weighed as x=0.8 and is dissolved in The citric acid solution of water white transparency is formed in 300mL deionized waters, according to mol ratio Li：V=3.0~3.2:1 to weigh 3.73g inclined Ammonium vanadate is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.99g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=0.8, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 13.89g butyl titanates, is dissolved in 2h is stirred in 100mL absolute ethyl alcohols, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs the water vinegar of 10.76g bis- Sour lithium is added thereto, and continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 120 DEG C of air dry ovens drying 24h, obtain 0.8Li3VO4·0.2Li4Ti5O12Composite material precursor；
(4) by (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h with stove from So cooling, takes out sample 700 DEG C of sintering 12h after grinding and obtains 0.8Li3VO4·0.2Li4Ti5O12Negative electrode of lithium ion battery Composite.
Embodiment 8
(1) according to chemical formula x Li3VO4·(1-x)Li4Ti5O12, citric acid 13.45g is weighed as x=8 and is dissolved in 300mL The citric acid solution of water white transparency is formed in deionized water, according to mol ratio Li：V=3.0~3.2:1 weighs 3.73g metavanadic acids Ammonium is slowly added into after magnetic agitation 1h is fully complexed under formation claret clear solution, normal temperature in citric acid solution and added 9.99g Lithium acetate dihydrates continue to stir formation clear solution A after 0.5h as lithium source；
(2) as x=8, according to mol ratio Li：Ti=4.0~4.1:5, which weigh 13.89g butyl titanates, is dissolved in 100mL 2h is stirred in absolute ethyl alcohol, under normal temperature and forms uniform butyl titanate ethanol solution, then weighs 10.76g Lithium acetate dihydrates It is added thereto, continues to stir formation shallow yellow transparent solution B after 1h；
(3) prepare after solution A and B, solution A is added drop-wise in solution B with 20mL/min speed and slowly hydrolyzed to form Yellow-green soln, is warming up to after 80 DEG C of evaporation solvent formation wet gels and is transferred to 100 DEG C of air dry ovens drying 24h, obtain 0.8Li3VO4·0.2Li4Ti5O12Composite material precursor；
(4) presoma will (3) be prepared in Muffle furnace with natural with stove after 3 DEG C/min heating rates, 450 DEG C of pre-burning 4h Cooling, takes out sample 900 DEG C of sintering 8h after grinding and obtains 0.8Li3VO4·0.2Li4Ti5O12Negative electrode of lithium ion battery is combined Material.
With reference to accompanying drawing, 0.75Li prepared by the present invention is illustrated with embodiment 13VO4·0.25Li4Ti5O12The thing of composite Mutually characterize and chemical property：
Fig. 1 is 0.75Li prepared by embodiment 13VO4·0.25Li4Ti5O12The XRD spectrum of composite, from analysis result From the point of view of composite mainly include Li3VO4Phase and Li4Ti5O12Phase, both diffraction maximums are all relatively strong, illustrate the crystallinity of material compared with It is high.In addition, there is some TiO2Mutually exist, illustrate TiO in sintering process2It is not fully converted to Li4Ti5O12Phase.
Fig. 2 is 0.75Li prepared by embodiment 13VO4·0.25Li4Ti5O12The SEM spectrum of composite, from analysis result From the point of view of composite be mainly the smooth spheric granules in surface, the particle diameter distribution of material is without bright between 200nm~3 μm, particle Aobvious duct, accumulates closely knit.
Fig. 3 is 0.75Li prepared by embodiment 13VO4·0.25Li4Ti5O12The first charge-discharge curve map of composite, From the point of view of compound anterioposterior curve contrast, the charge and discharge platform change of curve is obvious after lithium titanate is compound, the capacity of material Play higher, while finding that below 1.0V material discharging platforms are gentle, the main capacity of material is conducive to improving material in more than 0.1V The battery security of material.
Fig. 4 is 0.75Li prepared by embodiment 13VO4·0.25Li4Ti5O12The cyclic curve figure of composite, by multiple Close from the point of view of anterioposterior curve contrast, the cycle performance of material is significantly improved after lithium titanate is compound, by 150 circulations The capability retention of material is also maintained at more than 80%.

Claims (5)

1. a kind of composite cathode material of lithium ion battery, it is characterised in that：By Li3VO4And Li4Ti5O12Two-phase is according to chemical formula x Li3VO4·(1-x)Li4Ti5O12It is combined, wherein 0.5≤x ＜ 1；Its preparation method comprises the following steps：
(1) according to mol ratio Li：V=3.0~3.2:1 weighs lithium source and vanadium source, adds " complexing agent and solvent " and forms solution afterwards Or slurry A；
(2) according to mol ratio Li：Ti=4.0~4.1:5 weigh lithium source and titanium source, add and solution or slurry B are formed after solvent；
(3) after A and B is well mixed by the method for liquid phase, it is transferred to after being warming up to 70-90 DEG C of evaporation solvent formation wet gel Air dry oven dries 12~48h under the conditions of 80-120 DEG C, obtains Li3VO4And Li4Ti5O12Presoma；
(4) (3) are prepared into presoma in Muffle furnace in stove Temperature fall, taking out sample after 400-500 DEG C of pre-burning 3-5h Product are by grinding after 600~900 DEG C, and 6~12h of sintering obtains Li3VO4And Li4Ti5O12The compound lithium ion battery of two-phase is born Pole material.
2. composite cathode material of lithium ion battery according to claim 1, it is characterised in that the lithium source be lithium nitrate, One or both of lithium acetate, lithium hydroxide, lithium carbonate；Vanadium source is one kind in ammonium metavanadate or vanadic anhydride；Titanium source For one or both of butyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium dioxide, titanium tetrachloride.
3. composite cathode material of lithium ion battery according to claim 1, it is characterised in that the complexing agent in step (1) For organic acid；The organic acid be citric acid, glycine, salicylic acid, oxalic acid, adipic acid, ethylenediamine tetra-acetic acid in one kind or Several combinations.
4. composite cathode material of lithium ion battery according to claim 1, it is characterised in that the solvent is deionization Water, ethanol, ethylene glycol, the one or two of acetone.
5. composite cathode material of lithium ion battery according to claim 1, it is characterised in that the sintering atmosphere is sky Gas.
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