CN107994220A - LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified - Google Patents

LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified Download PDF

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CN107994220A
CN107994220A CN201711214440.7A CN201711214440A CN107994220A CN 107994220 A CN107994220 A CN 107994220A CN 201711214440 A CN201711214440 A CN 201711214440A CN 107994220 A CN107994220 A CN 107994220A
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molybdenum
limn
modified
doping
limn2o4
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何苗
冯叶锋
王成民
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Guangdong University of Technology
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Guangdong University of Technology
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Priority to PCT/CN2018/087208 priority patent/WO2019104948A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/50—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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  • Secondary Cells (AREA)

Abstract

The present invention provides the LiMn2O4 composite material that a kind of molybdenum doping is modified, and is that surface is coated with the LiMn2O4 that the molybdenum doping of carbon is modified, the LiMn2O4 that the molybdenum doping is modified has chemical formula shown in Formulas I：LiMn2‑xMoxO4Formulas I；Wherein, 0.01≤x≤0.1；The mass fraction of carbon is 0.1~20%；LiMn2‑xMoxO4Mass fraction be 80~99.9%.The present invention is doped LiMn2O4 using molybdenum, can effectively suppress spinel structure LiMn2O4Jahn Teller effects and manganese dissolving, so as to improve cyclical stability and high-temperature behavior.A kind of preparation method for the LiMn2O4 composite material being modified present invention also offers molybdenum doping, this method simple process and low cost is environmental-friendly, suitable for large-scale industrial production.

Description

LiMn2O4 composite material, its preparation method and the lithium ion that a kind of molybdenum doping is modified Battery
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of molybdenum doping be modified LiMn2O4 composite material, Its preparation method and lithium ion battery.
Background technology
Lithium ion battery due to operating voltage is high, energy density is big, have extended cycle life, self-discharge rate is low, low stain, The excellent properties such as memory-less effect, are widely used in the portable electrics such as mobile phone, laptop, tablet computer, camera In sub- equipment.Grow to even greater heights with the strengthening of people's awareness of environmental protection with oil price, the new energy such as electric bicycle, electric automobile Source industry has good development prospect, and lithium ion battery with above many merits as electric automobile is preferred because move Power battery.But lithium ion battery is as power battery, still face the problems such as due to security performance, energy density, power density Face the challenge of many, therefore the lithium ion battery for meeting power battery requirement need be developed.
Anode material for lithium-ion batteries is an important component of lithium ion battery, great on battery performance influence, Wherein LiMn2O4 due to have the advantages that aboundresources, it is cheap, nontoxic receive significant attention, the application in power battery Very advantageous, but spinelle LiMn2O4Material has the shortcomings that fatal, and capacity attenuation is very fast, under high temperature (55 DEG C) particularly such as This.
The content of the invention
It is an object of the invention to provide LiMn2O4 composite material, its preparation method and the lithium ion that a kind of molybdenum doping is modified Battery, the present invention in molybdenum doping be modified LiMn2O4 composite material there is preferable cycle performance.
The present invention provides the LiMn2O4 composite material that a kind of molybdenum doping is modified, and the molybdenum doping modification of carbon is coated with for surface LiMn2O4,
The LiMn2O4 that the molybdenum doping is modified has chemical formula shown in Formulas I：
LiMn2-xMoxO4Formulas I；
Wherein, 0.01≤x≤0.1；
The mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4Mass fraction be 80~99.9%.
The present invention provides a kind of preparation method for the LiMn2O4 composite material that molybdenum doping is modified, and comprises the following steps：
A) organic acid, lithium salt solution and manganese salt solution are mixed, obtain mixed solution；
B) molybdenum source is added in mixed solution, obtains doped solution；Manganese rubs in molybdenum and manganese salt solution in the molybdenum source Your ratio is x：(2-x), wherein, 0.01≤x≤0.1；
C) doped solution is heated successively, dry and ball mill crushing, obtains powder body material；
D) powder body material is sintered, obtains having the LiMn of structure shown in Formulas I2-xMoxO4Material；
LiMn2-xMoxO4/ C Formulas I；
Wherein, 0.01≤x≤0.1；
E) by carbon source and LiMn2-xMoxO4It is sintered after material mixing, obtains the mangaic acid lithium composite of molybdenum doping modification Material；
In the LiMn2O4 composite material that the molybdenum doping is modified, the mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4's Mass fraction is 80~99.9%.
Preferably, the lithium salts is lithium hydroxide, the one or more in lithium carbonate and lithium acetate；
Manganese salt is the one or more in manganese nitrate, manganese sulfate and manganese acetate；
The organic acid is the one or more in citric acid, glucose, sucrose, starch, tartaric acid and glycine；
The molar ratio of the organic acid and manganese in manganese salt is (1~5)：1.
Preferably, the molybdenum source is the one or more in sodium molybdate, molybdenum acid ammonia, magnesium molybdate and potassium molybdate.
Preferably, the step C) in heating temperature be 80~150 DEG C；
The step C) in heating time for 8~20 it is small when.
Preferably, the step C) in dry temperature be 80~120 DEG C；
The step C) in dry time for 10~20 it is small when.
Preferably, the step D) in sintering be specially：
The powder body material is risen to 450~550 DEG C with the heating rate of 1~5 DEG C/min from room temperature, sintering 3~10 is small When；Then with the heating rate of 1~5 DEG C/min be warming up to 650~950 DEG C insulation 8~24 it is small when, obtain LiMn2-xMoxO4Material Material.
Preferably, the carbon source and LiMn2-xMoxO4The mass ratio of material is (0.1~0.5)：1.
Preferably, the step E) in sintering be specially：
By carbon source and LiMn2-xMoxO4After material mixing, 650~850 are risen to from room temperature with the heating rate of 1~5 DEG C/min DEG C, when insulation 10~20 is small, the LiMn2O4 composite material that obtains having the molybdenum doping of structure shown in Formulas I to be modified.
The present invention provides a kind of lithium ion battery, and the positive electrode is answered for the LiMn2O4 that molybdenum doping described above is modified Condensation material.
Applicant is it has been investigated that several possible mechanism cause capacity attenuation：(1) it is abnormal that lattice occurs in charge and discharge process Become, i.e. Jahn-Teller effects, cause LiMn2O4The contraction of cathode material structure and expansion are to cause the important original of capacity attenuation Cause.(2) one of the reason for dissolving of manganese is also capacity attenuation.Due to containing Mn in spinelle3+, discrimination can occur in acid condition Change reaction：2Mn3+=Mn4++Mn2+, Mn2+Then it is dissolvable in water in electrolyte, so that the reduction of active material is caused, and in high temperature bar Under part, disproportionated reaction speed is faster.(3) change caused by Jahn-Teller effects from cubic system to the structure of tetragonal crystal system The passage of lithium ion disengaging is hindered, so that capacity attenuation.(4) crystallinity of synthetic material, granular size and pattern, particle diameter Distribution etc. can all influence LiMn2O4Chemical property.(5)LiMn2O4With higher charge and discharge platform, electrolyte is in high electricity Depress easy oxygenolysis.(6) it is improper to use battery, as super-charge super-discharge can all influence battery performance.
The present invention provides the LiMn2O4 composite material that a kind of molybdenum doping is modified, the molybdenum doping that carbon is coated with for surface is modified LiMn2O4, the LiMn2O4 that the molybdenum doping is modified has chemical formula shown in Formulas I：LiMn2-xMoxO4Formulas I；Wherein, 0.01≤x≤ 0.1；The mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4Mass fraction be 80~99.9%.The present invention is using molybdenum to manganese Sour lithium is doped, and can effectively suppress spinel structure LiMn2O4Jahn-Teller effects and manganese dissolving, so as to improve Cyclical stability and high-temperature behavior.
A kind of preparation method for the LiMn2O4 composite material being modified present invention also offers molybdenum doping, the present invention is according to certain Proportioning addition lithium source, manganese source doped source (molybdenum) and add deionized water and are mixed, at a certain temperature, be slowly evaporated, most After form gel, molybdenum (Mo) doping vario-property spinel structure LiMn can be obtained after oversintering2-xMoxO4/ C composite.Institute Preparing material has excellent electrochemical performance, shows excellent cycling stabilization and high-temperature behavior.This method technique is simple, cost It is low, it is environmental-friendly, suitable for large-scale industrial production.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are only this The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis The attached drawing of offer obtains other attached drawings.
Fig. 1 is LiMn in the embodiment of the present invention 12-xMoxO4The XRD diagram of/C composite；
Fig. 2 is LiMn in the embodiment of the present invention 12-xMoxO4The SEM figures of/C；
Fig. 3 is pure LiMn in the embodiment of the present invention 12O4SEM figure；
Fig. 4 is molybdenum (Mo) doping vario-property spinel structure LiMn in the embodiment of the present invention 12-xMoxO4/ C composite is not With charging and discharging curve under multiplying power；
Fig. 5 is molybdenum (Mo) doping vario-property spinel structure LiMn in the embodiment of the present invention 12-xMoxO4/ C composite is followed Ring performance curve.
Embodiment
The present invention provides the LiMn2O4 composite material that a kind of molybdenum doping is modified, and the molybdenum doping modification of carbon is coated with for surface LiMn2O4,
The LiMn2O4 that the molybdenum doping is modified has chemical formula shown in Formulas I：
LiMn2-xMoxO4Formulas I；
Wherein, 0.01≤x≤0.1；The mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4Mass fraction for 80~ 99.9%.
In the present invention, the x is preferably 0.01,0.05,0.08 or 0.1；The mass fraction of C is preferably 1~15%, more Preferably 5~10%；The LiMn2-xMoxO4Mass fraction be preferably 85~99%, more preferably 90~95%.
A kind of preparation method for the LiMn2O4 composite material being modified present invention also offers molybdenum doping, comprises the following steps：
A) organic acid, lithium salt solution and manganese salt solution are mixed, obtain mixed solution；
B) molybdenum source is added in mixed solution, obtains doped solution；Manganese rubs in molybdenum and manganese salt solution in the molybdenum source Your ratio is x：(2-x), wherein, 0.01≤x≤0.1；
C) doped solution is heated successively, dry and ball mill crushing, obtains powder body material；
D) powder body material is sintered, obtains having the LiMn of structure shown in Formulas I2-xMoxO4Material；
LiMn2-xMoxO4/ C Formulas I；
Wherein, 0.01≤x≤0.1；
E) by carbon source and LiMn2-xMoxO4It is sintered after material mixing, obtains the mangaic acid lithium composite of molybdenum doping modification Material；
In the LiMn2O4 composite material that the molybdenum doping is modified, the mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4's Mass fraction is 80~99.9%.
Lithium salts and manganese salt are preferably dissolved in deionized water by the present invention respectively, are configured to lithium salt solution and manganese salt solution, then The lithium salt solution and manganese salt solution are mixed, organic acid is then added, obtains mixed solution.
In the present invention, the lithium salts is lithium hydroxide, the one or more in lithium carbonate and lithium acetate；Manganese salt is nitric acid One or more in manganese, manganese sulfate and manganese acetate；The organic acid for citric acid, glucose, sucrose, starch, tartaric acid and One or more in glycine；The molar ratio of the organic acid and manganese in manganese salt is preferably (1~5)：1, more preferably (2~ 4)：1, specifically, can be 1:1、2:1、3:1、4:1 or 5:1.The lithium salts and manganese salt according to the stoichiometric ratio in Formulas I into Row addition.
Molybdenum source is added in above-mentioned mixed solution, when stirring 1~2 is small, obtains doped solution, the molybdenum source is preferably molybdic acid One or more in sodium, molybdenum acid ammonia, magnesium molybdate and potassium molybdate；The molybdenum source and the molar ratio of manganese in manganese source are preferably (2-x)： X, 0.01≤x≤0.1, the x are preferably 0.01,0.05,0.08 or 0.1.
The present invention heats above-mentioned doped solution, and water therein is all evaporated, obtains gelatinous mass, then will be described solidifying Glue material is dried, then dried object is carried out ball mill crushing, obtains broken powder.
In the present invention, the temperature of the heating is preferably 80~150 DEG C, more preferably 90~140 DEG C, specifically, can To be 80 DEG C, 90 DEG C, 115 DEG C, 140 DEG C or 150 DEG C；When the time of the heating is preferably 8~20 small, more preferably 10~17 Hour, specifically, when can be 8 small, 10 it is small when, 14 it is small when, 17 it is small when or 20 it is small when.The temperature of the drying is preferably 80~ 120 DEG C, more preferably 90~110 DEG C, specifically, can be 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C；The drying When time is preferably 10~20 small, more preferably 12~16 it is small when, specifically, when can be 10 small, 12 it is small when, 14 it is small when, 16 Hour or 20 it is small when.
The present invention be raised to preferably by broken powder body material from 25 DEG C with 1~5 DEG C/min in air atmosphere 450~550 DEG C, Preferably 470~500 DEG C, 3~10h is sintered, is preferably 4~8h, more preferably 6.5h；Then again in air atmosphere with 1~5 DEG C/min is raised to 650~950 DEG C, it is preferably 700~900 DEG C, more preferably 750~850 DEG C, keeps the temperature 8~24h, preferably 12~ 20h, more preferably 15~16 it is small when；Cooled to room temperature obtains molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4Material Material.
Carbon source is preferably dissolved in deionized water by the present invention, then adds above-mentioned LiMn2-xMoxO4Material, after stirring evenly, It is transferred in ball grinder, then adds the deionized water of raw material solid content 10~60%, be put into agate pearl, carries out ball milling, Uniform slurry is obtained, is then dried successively, ball mill crushing and sintering.
In the present invention, the carbon source and LiMn2-xMoxO4The mass ratio of material is preferably (0.1~0.5)：1, more preferably For (0.2~0.4)：1；The mass ratio of the agate pearl and material in ball grinder is preferably (1~5)：1, more preferably (2~ 4)：1；The rotating speed of the ball milling is preferably 200~500rpm/min, more preferably 300~400rpm/min；The ball milling when Between be preferably 5~12 it is small when, more preferably 8~10 it is small when.
In the present invention, the temperature of the drying is preferably 80~120 DEG C, more preferably 90~110 DEG C, is most preferably 100℃；When the time of the drying is preferably 5~12 small, more preferably 8~10 it is small when.
In the present invention, the sintering is preferably under protective gas atmosphere, with the heating rate of 1~5 DEG C/min from room Warm (i.e. 25 DEG C) rise to 650~850 DEG C, when insulation 10~20 is small, obtain the LiMn2O4 composite material (LiMn of molybdenum doping modification2- xMoxO4/C)。
The temperature of the sintering is preferably 700~800 DEG C, the specific can be 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C or 850℃；When the time of the insulation is preferably 12~18 small, the specific can be 10 it is small when, 12 it is small when, 15 it is small when, 18 it is small when Or 20 it is small when.
The protective gas is preferably nitrogen and/or argon gas.
Present invention also offers a kind of lithium ion battery, the positive electrode of the lithium ion battery is the molybdenum doping in the present invention Modified LiMn2O4 composite material.In the present invention, the other parts of the lithium ion battery, such as anode, membrane, electrolyte Part can use the common material of those skilled in the art, and as anode uses metal lithium sheet, membrane uses polypropylene, electrolyte Using LiPF6；Conductive agent uses carbon black SuperP, and binding agent uses PVDF.
The present invention is preferably according to 90：5：5 ratio is by the molybdenum prepared (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite, conductive black SuperP, binding agent PVDF mixing, adds N- methyl arsenic pyrrolidones, stirs 12h.Gained Mixture paste coated on aluminium foil, dry 12h obtains positive plate in 120 DEG C of vacuum drying chambers.Just extremely molybdenum (Mo) is mixed Miscellaneous modified spinelle structure LiMn2-xMoxO4/ C composite and pure LiMn2O4Positive electrode, anode are metal lithium sheet, and membrane is Polypropylene, LiPF6For electrolyte, battery assembling is carried out in the glove box full of argon gas, obtains lithium ion battery.
The present invention provides the LiMn2O4 composite material that a kind of molybdenum doping is modified, the molybdenum doping that carbon is coated with for surface is modified LiMn2O4, the LiMn2O4 that the molybdenum doping is modified has chemical formula shown in Formulas I：LiMn2-xMoxO4Formulas I；Wherein, 0.01≤x≤ 0.1；The mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4Mass fraction be 80~99.9%.The present invention is using molybdenum to manganese Sour lithium is doped, and can effectively suppress spinel structure LiMn2O4Jahn-Teller effects and manganese dissolving, so as to improve Cyclical stability and high-temperature behavior.
A kind of preparation method for the LiMn2O4 composite material being modified present invention also offers molybdenum doping, the present invention is according to certain Proportioning addition lithium source, manganese source doped source (molybdenum) and add deionized water and are mixed, at a certain temperature, be slowly evaporated, most After form gel, molybdenum (Mo) doping vario-property spinel structure LiMn can be obtained after oversintering2-xMoxO4/ C composite.Institute Preparing material has excellent electrochemical performance, shows excellent cycling stabilization and high-temperature behavior.This method technique is simple, cost It is low, it is environmental-friendly, suitable for large-scale industrial production.
In order to further illustrate the present invention, the mangaic acid being modified with reference to embodiments to a kind of molybdenum doping provided by the invention Lithium composite material, its preparation method and lithium ion battery are described in detail, but cannot be understood as protecting model to the present invention The restriction enclosed.
Embodiment 1
1. weigh a certain amount of lithium salts according to molar ratio shown in manganate cathode material for lithium chemical formula and manganese salt be dissolved in from In sub- water, it is configured to concentration and is the aqueous solution of 0.05mol/L, and above solution is mixed.
2. it is 1 according to transition metal manganese and organic acid molar ratio：Organic acid is added in above-mentioned mixed solution by 1 amount.
3. it is 1.99 according to manganese source and molybdenum source molar ratio：0.01 adds molybdenum source in above-mentioned mixed solution, is stirred 1h.
4. the mixed solution of above-mentioned acquisition stirs 8h at 80 DEG C, until deionized water is all evaporated, gelatinous mass is obtained, Then it is put into drying box after 80 DEG C of dry 10h, takes out dried object and carry out ball mill crushing.
5. broken powder body material is finally raised to 450 DEG C of sintering 10h in air atmosphere with 1 DEG C/min from 25 DEG C, then 650 DEG C of insulation 24h are raised to 1 DEG C/min in air atmosphere again, it is brilliant that cooled to room temperature obtains molybdenum (Mo) doping vario-property point Stone structure LiMn2-xMoxO4Material.
6. by LiMn2-xMoxO4The carbon source of content 10% is dissolved in deionized water, adds molybdenum (Mo) doping obtained by step 5 Modified spinelle structure LiMn2-xMoxO4Material stirs, and is transferred in ball grinder, while add going for raw material solid content 10% Ionized water and it is put into agate pearl (quality of material ratio and pearl is 1：1).Ball milling 12h, obtains under 200rpm/min rotating speeds Uniform sizing material material, is then put into drying box after 80 DEG C of dry 12h, takes out dried object and carries out ball mill crushing.
7. broken powder body material is finally raised to 650 DEG C of insulation 10h, nature with 1 DEG C/min from 25 DEG C in an inert atmosphere It is cooled to room temperature to obtain molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite.
To molybdenum (Mo) the doping vario-property spinel structure LiMn of the gained of embodiment 12-xMoxO4/ C composite and embodiment 1 The pure LiMn of middle gained2O4The phase structure and microstructure of positive electrode are characterized.As shown in Figure 1, Fig. 1 is real for the present invention Apply LiMn in example 12-xMoxO4The XRD diagram of/C composite.As known to XRD diagram, molybdenum (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite keeps spinel structure, with pure LiMn2O4The diffraction maximum of positive electrode is similar, and dephasign does not occur Peak, this explanation molybdenum (Mo) doping and carbon coating do not influence LiFePO4Phase structure.
1 molybdenum of the present embodiment (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite and gained in embodiment 1 Pure LiMn2O4The SEM figures of positive electrode are contrasted, and as shown in figures 2-3, find LiMn2O4Molybdenum (Mo) adulterates and carbon coating Modified, its microstructure does not change.
By embodiment 1 according to 90：5：5 ratio is by the molybdenum prepared (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite, conductive black SuperP, binding agent PVDF mixing, adds N- methyl arsenic pyrrolidones, stirs 12h.Gained Mixture paste coated on aluminium foil, dry 12h obtains positive plate in 120 DEG C of vacuum drying chambers.Just extremely molybdenum (Mo) is mixed Miscellaneous modified spinelle structure LiMn2-xMoxO4/ C composite and pure LiMn2O4Positive electrode, anode are metal lithium sheet, and membrane is Polypropylene, LiPF6For electrolyte, battery assembling is carried out in the glove box full of argon gas, then carries out electrochemical property test.
Fig. 4 is molybdenum (Mo) doping vario-property spinel structure LiMn made from embodiment 12-xMoxO4/ C composite is in difference Charging and discharging curve under multiplying power.As shown in Figure 4, molybdenum (Mo) doping vario-property spinel structure LiMn is made by embodiment 12-xMoxO4/C Composite material exhibits go out excellent high rate performance, under 0.1C and 5C multiplying powers specific discharge capacity be respectively 132.3mAh/g and 113.8mAh/g。
By Fig. 5 it can be seen that molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4The performance of/C composite preferably follows Ring stability, 95.2% can be reached by under 5C multiplying powers circulating 100 capacity retention ratios.
Embodiment 2
1. weigh a certain amount of lithium salts according to molar ratio shown in manganate cathode material for lithium chemical formula and manganese salt be dissolved in from In sub- water, it is configured to concentration and is the aqueous solution of 0.5mol/L, and above solution is mixed.
2. it is 1 according to transition metal manganese and organic acid molar ratio：Organic acid is added in above-mentioned mixed solution by 2 amount.
3. it is 1.95 according to manganese source and molybdenum source molar ratio：0.05 adds molybdenum source in above-mentioned mixed solution, is stirred 1.2h。
4. the mixed solution of above-mentioned acquisition stirs 10h at 90 DEG C, until deionized water is all evaporated, jello is obtained Matter, is then put into drying box after 90 DEG C of dry 12h, takes out dried object and carries out ball mill crushing.
5. broken powder body material is finally raised to 470 DEG C of sintering 4h, Ran Houzai in air atmosphere with 2 DEG C/min from 25 DEG C 700 DEG C of insulation 10h are raised to 2 DEG C/min in air atmosphere, cooled to room temperature obtains molybdenum (Mo) doping vario-property spinelle Structure LiMn2-xMoxO4Material.
6. by LiMn2-xMoxO4The carbon source of content 20% is dissolved in deionized water, adds molybdenum (Mo) doping obtained by step 5 Modified spinelle structure LiMn2-xMoxO4Material stirs, and is transferred in ball grinder, while add going for raw material solid content 20% Ionized water and it is put into agate pearl (quality of material ratio and pearl is 1：2).The ball milling 7h under 300rpm/min rotating speeds, obtains Even slurry material, is then put into drying box after 90 DEG C of dry 8h, takes out dried object and carries out ball mill crushing.
7. broken powder body material is finally raised to 700 DEG C of insulation 12h, nature with 2 DEG C/min from 25 DEG C in an inert atmosphere It is cooled to room temperature to obtain molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite.
By embodiment 2 according to 90：5：5 ratio is by the molybdenum prepared (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite, conductive black SuperP, binding agent PVDF mixing, adds N- methyl arsenic pyrrolidones, stirs 12h.Gained Mixture paste coated on aluminium foil, dry 12h obtains positive plate in 120 DEG C of vacuum drying chambers.Just extremely molybdenum (Mo) is mixed Miscellaneous modified spinelle structure LiMn2-xMoxO4/ C composite and pure LiMn2O4Positive electrode, anode are metal lithium sheet, and membrane is Polypropylene, LiPF6For electrolyte, battery assembling is carried out in the glove box full of argon gas.At 25 DEG C, between 3.0~4.3V Carry out electrochemical property test, the results showed that molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite have compared with Height ratio capacity, stable circulation, excellent high rate performance, shows excellent electrochemical performance.
Embodiment 3
1. weigh a certain amount of lithium salts according to molar ratio shown in manganate cathode material for lithium chemical formula and manganese salt be dissolved in from In sub- water, it is configured to concentration and is the aqueous solution of 1.53mol/L, and above solution is mixed.
2. it is 1 according to transition metal manganese and organic acid molar ratio：Organic acid is added in above-mentioned mixed solution by 3 amount.
3. it is 1.95 according to manganese source and molybdenum source molar ratio：0.05 adds molybdenum source in above-mentioned mixed solution, is stirred 1.5h。
4. the mixed solution of above-mentioned acquisition stirs 14h at 115 DEG C, until deionized water is all evaporated, jello is obtained Matter, is then put into drying box after 100 DEG C of dry 15h, takes out dried object and carries out ball mill crushing.
5. broken powder body material is finally raised to 500 DEG C of sintering 6.5h in air atmosphere with 3 DEG C/min from 25 DEG C, then 800 DEG C of insulation 16h are raised to 3 DEG C/min in air atmosphere again, it is brilliant that cooled to room temperature obtains molybdenum (Mo) doping vario-property point Stone structure LiMn2-xMoxO4Material.
6. by LiMn2-xMoxO4The carbon source of content 30% is dissolved in deionized water, adds molybdenum (Mo) doping obtained by step 5 Modified spinelle structure LiMn2-xMoxO4Material stirs, and is transferred in ball grinder, while add going for raw material solid content 35% Ionized water and it is put into agate pearl (quality of material ratio and pearl is 1：3).Ball milling 8.5h, obtains under 350rpm/min rotating speeds Uniform sizing material material, is then put into drying box after 100 DEG C of dry 8.5h, takes out dried object and carries out ball mill crushing.
7. broken powder body material is finally raised to 750 DEG C of insulation 15h, nature with 3 DEG C/min from 25 DEG C in an inert atmosphere It is cooled to room temperature to obtain molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite.
By embodiment 3 according to 90：5：5 ratio is by the molybdenum prepared (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite, conductive black SuperP, binding agent PVDF mixing, adds N- methyl arsenic pyrrolidones, stirs 12h.Gained Mixture paste coated on aluminium foil, dry 12h obtains positive plate in 120 DEG C of vacuum drying chambers.Just extremely molybdenum (Mo) is mixed Miscellaneous modified spinelle structure LiMn2-xMoxO4/ C composite and pure LiMn2O4Positive electrode, anode are metal lithium sheet, and membrane is Polypropylene, LiPF6For electrolyte, battery assembling is carried out in the glove box full of argon gas.At 25 DEG C, between 3.0~4.3V Carry out electrochemical property test, the results showed that molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite have compared with Height ratio capacity, stable circulation, excellent high rate performance, shows excellent electrochemical performance.
Embodiment 4
1. weigh a certain amount of lithium salts according to molar ratio shown in manganate cathode material for lithium chemical formula and manganese salt be dissolved in from In sub- water, it is configured to concentration and is the aqueous solution of 2mol/L, and above solution is mixed.
2. it is 1 according to transition metal manganese and organic acid molar ratio：Organic acid is added in above-mentioned mixed solution by 4 amount.
3. it is 1.92 according to manganese source and molybdenum source molar ratio：0.08 adds molybdenum source in above-mentioned mixed solution, is stirred 1.8h。
4. the mixed solution of above-mentioned acquisition stirs 17h at 140 DEG C, until deionized water is all evaporated, jello is obtained Matter, is then put into drying box after 110 DEG C of dry 16h, takes out dried object and carries out ball mill crushing.
5. broken powder body material is finally raised to 560 DEG C of sintering 8h, Ran Houzai in air atmosphere with 4 DEG C/min from 25 DEG C 900 DEG C of insulation 15h are raised to 4 DEG C/min in air atmosphere, cooled to room temperature obtains molybdenum (Mo) doping vario-property spinelle Structure LiMn2-xMoxO4Material.
6. by LiMn2-xMoxO4The carbon source of content 40% is dissolved in deionized water, adds molybdenum (Mo) doping obtained by step 5 Modified spinelle structure LiMn2-xMoxO4Material stirs, and is transferred in ball grinder, while add going for raw material solid content 50% Ionized water and it is put into agate pearl (quality of material ratio and pearl is 1：4).Ball milling 10h, obtains under 400rpm/min rotating speeds Uniform sizing material material, is then put into drying box after 110 DEG C of dry 10h, takes out dried object and carries out ball mill crushing.
7. broken powder body material is finally raised to 800 DEG C of insulation 18h, nature with 4 DEG C/min from 25 DEG C in an inert atmosphere It is cooled to room temperature to obtain molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite.
By embodiment 4 according to 90：5：5 ratio is by the molybdenum prepared (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite, conductive black SuperP, binding agent PVDF mixing, adds N- methyl arsenic pyrrolidones, stirs 12h.Gained Mixture paste coated on aluminium foil, dry 12h obtains positive plate in 120 DEG C of vacuum drying chambers.Just extremely molybdenum (Mo) is mixed Miscellaneous modified spinelle structure LiMn2-xMoxO4/ C composite and pure LiMn2O4Positive electrode, anode are metal lithium sheet, and membrane is Polypropylene, LiPF6For electrolyte, battery assembling is carried out in the glove box full of argon gas.At 25 DEG C, between 3.0~4.3V Carry out electrochemical property test, the results showed that molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite have compared with Height ratio capacity, stable circulation, excellent high rate performance, shows excellent electrochemical performance.
Embodiment 5
1. weigh a certain amount of lithium salts according to molar ratio shown in manganate cathode material for lithium chemical formula and manganese salt be dissolved in from In sub- water, it is configured to concentration and is the aqueous solution of 3mol/L, and above solution is mixed.
2. it is 1 according to transition metal manganese and organic acid molar ratio：Organic acid is added in above-mentioned mixed solution by 5 amount.
3. it is 1.9 according to manganese source and molybdenum source molar ratio：0.1 adds molybdenum source in above-mentioned mixed solution, is stirred 2h.
4. the mixed solution of above-mentioned acquisition stirs 20h at 150 DEG C, until deionized water is all evaporated, jello is obtained Matter, is then put into drying box after 120 DEG C of dry 20h, takes out dried object and carries out ball mill crushing.
5. broken powder body material is finally raised to 550 DEG C of sintering 10h in air atmosphere with 5 DEG C/min from 25 DEG C, then 950 DEG C of insulation 24h are raised to 5 DEG C/min in air atmosphere again, it is brilliant that cooled to room temperature obtains molybdenum (Mo) doping vario-property point Stone structure LiMn2-xMoxO4Material.
6. by LiMn2-xMoxO4The carbon source of content 50% is dissolved in deionized water, adds molybdenum (Mo) doping obtained by step 5 Modified spinelle structure LiMn2-xMoxO4Material stirs, and is transferred in ball grinder, while add going for raw material solid content 60% Ionized water and it is put into agate pearl (quality of material ratio and pearl is 1：5).Ball milling 12h, obtains under 500rpm/min rotating speeds Uniform sizing material material, is then put into drying box after 120 DEG C of dry 12h, takes out dried object and carries out ball mill crushing.
7. broken powder body material is finally raised to 850 DEG C of insulation 10h, nature with 5 DEG C/min from 25 DEG C in an inert atmosphere It is cooled to room temperature to obtain molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite.
By embodiment 5 according to 90：5：5 ratio is by the molybdenum prepared (Mo) doping vario-property spinel structure LiMn2- xMoxO4/ C composite, conductive black SuperP, binding agent PVDF mixing, adds N- methyl arsenic pyrrolidones, stirs 12h.Gained Mixture paste coated on aluminium foil, dry 12h obtains positive plate in 120 DEG C of vacuum drying chambers.Just extremely molybdenum (Mo) is mixed Miscellaneous modified spinelle structure LiMn2-xMoxO4/ C composite and pure LiMn2O4Positive electrode, anode are metal lithium sheet, and membrane is Polypropylene, LiPF6For electrolyte, battery assembling is carried out in the glove box full of argon gas.At 25 DEG C, between 3.0~4.3V Carry out electrochemical property test, the results showed that molybdenum (Mo) doping vario-property spinel structure LiMn2-xMoxO4/ C composite have compared with Height ratio capacity, stable circulation, excellent high rate performance, shows excellent electrochemical performance.
The above is only the 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 also should It is considered as protection scope of the present invention.

Claims (10)

1. the LiMn2O4 composite material that a kind of molybdenum doping is modified, the LiMn2O4 of the molybdenum doping modification of carbon is coated with for surface,
The LiMn2O4 that the molybdenum doping is modified has chemical formula shown in Formulas I：
LiMn2-xMoxO4Formulas I；
Wherein, 0.01≤x≤0.1；
The mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4Mass fraction be 80~99.9%.
2. a kind of preparation method for the LiMn2O4 composite material that molybdenum doping is modified, comprises the following steps：
A) organic acid, lithium salt solution and manganese salt solution are mixed, obtain mixed solution；
B) molybdenum source is added in mixed solution, obtains doped solution；The molar ratio of manganese in molybdenum and manganese salt solution in the molybdenum source For x：(2-x), wherein, 0.01≤x≤0.1；
C) doped solution is heated successively, dry and ball mill crushing, obtains powder body material；
D) powder body material is sintered, obtains having the LiMn of structure shown in Formulas I2-xMoxO4Material；
LiMn2-xMoxO4/ C Formulas I；
Wherein, 0.01≤x≤0.1；
E) by carbon source and LiMn2-xMoxO4It is sintered after material mixing, obtains the LiMn2O4 composite material of molybdenum doping modification；
In the LiMn2O4 composite material that the molybdenum doping is modified, the mass fraction of carbon is 0.1~20%；LiMn2-xMoxO4Quality Fraction is 80~99.9%.
3. preparation method according to claim 2, it is characterised in that the lithium salts is lithium hydroxide, lithium carbonate and acetic acid One or more in lithium；
Manganese salt is the one or more in manganese nitrate, manganese sulfate and manganese acetate；
The organic acid is the one or more in citric acid, glucose, sucrose, starch, tartaric acid and glycine；
The molar ratio of the organic acid and manganese in manganese salt is (1~5)：1.
4. preparation method according to claim 2, it is characterised in that the molybdenum source for sodium molybdate, molybdenum acid ammonia, magnesium molybdate and One or more in potassium molybdate.
5. preparation method according to claim 2, it is characterised in that the step C) in heating temperature be 80~150 ℃；
The step C) in heating time for 8~20 it is small when.
6. preparation method according to claim 2, it is characterised in that the step C) in dry temperature be 80~120 ℃；
The step C) in dry time for 10~20 it is small when.
7. preparation method according to claim 2, it is characterised in that the step D) in sintering be specially：
The powder body material is risen to 450~550 DEG C, when sintering 3~10 is small with the heating rate of 1~5 DEG C/min from room temperature；So Afterwards with the heating rate of 1~5 DEG C/min be warming up to 650~950 DEG C insulation 8~24 it is small when, obtain LiMn2-xMoxO4Material.
8. preparation method according to claim 2, it is characterised in that the carbon source and LiMn2-xMoxO4The mass ratio of material For (0.1~0.5)：1.
9. preparation method according to claim 2, it is characterised in that the step E) in sintering be specially：
By carbon source and LiMn2-xMoxO4After material mixing, 650~850 DEG C are risen to from room temperature with the heating rate of 1~5 DEG C/min, When insulation 10~20 is small, the LiMn2O4 composite material that obtains having the molybdenum doping of structure shown in Formulas I to be modified.
10. a kind of lithium ion battery, it is characterised in that the positive electrode is the mangaic acid that the molybdenum doping in claim 1 is modified The mangaic acid cathode of lithium material that molybdenum doping made from preparation method described in lithium titanate cathode material or claim 2~9 any one is modified Material.
CN201711214440.7A 2017-11-28 2017-11-28 LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified Pending CN107994220A (en)

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