CN108899523A - A kind of lithium ion battery nucleocapsid positive electrode and preparation method thereof - Google Patents

A kind of lithium ion battery nucleocapsid positive electrode and preparation method thereof Download PDF

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CN108899523A
CN108899523A CN201810745388.6A CN201810745388A CN108899523A CN 108899523 A CN108899523 A CN 108899523A CN 201810745388 A CN201810745388 A CN 201810745388A CN 108899523 A CN108899523 A CN 108899523A
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lithium
manganese
nucleome
preparation
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赵红远
王占奎
苏建修
李勇峰
吴婷婷
李芳�
李冬冬
王亚霜
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Henan Institute of Science and Technology
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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
    • H01M4/485—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
    • H01M4/48—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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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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Abstract

Present invention relates particularly to a kind of nucleocapsid positive electrodes and preparation method thereof.Nucleocapsid positive electrode provided by the invention, in traditional positive electrode LiMn2O4High-valence state silicon, titanium or zirconium are adulterated in core, with LiMn2‑xMxO4As nucleome, Mn in conventional lower valency doping vario-property is avoided3+The reduction of ion, and oxygen defect is inhibited, while improving the diffusivity of lithium ion to a certain extent；Shell Li2MO3As Shell Materials, nucleome is coated, realize the isolation to nucleome active material and electrolyte, the direct contact of the two can be reduced, to restrained effectively the dissolution of manganese in the electrolytic solution in nucleome, the diffusivity of lithium ion is further improved simultaneously, and then excellent high temperature circulation performance for stability can be shown.Embodiment the result shows that, capacity retention ratio is up to 95.1% after lithium ion battery nucleocapsid positive electrode provided by the invention recycles 100 times under the conditions of 55 DEG C.

Description

A kind of lithium ion battery nucleocapsid positive electrode and preparation method thereof
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of lithium ion battery nucleocapsid anode material Material and preparation method thereof.
Background technique
Electrochmical power source is formd as realizing that it is more mature that energy system of the chemical energy with electric energy conversion and storage has developed A plurality of heavy-duty battery products, such as widely applied lead-acid battery and nickel-cadmium cell product system.Although these traditional changes Learning power supply has quality stabilization, high reliability, but can generate during battery product manufacture more serious Environmental pollution, especially waste battery are dealt with improperly to destruction caused by environment for human survival, and the mankind can be seriously threatened Life and health.In contrast, lithium ion battery not only has traditional chemical power supply as a kind of novel electrochmical power source system Good characteristic, while it can be largely avoided the environment of the product systems such as traditional lead acid batteries and nickel-cadmium cell initiation again The serious problems such as pollution, by concern more and more extensive both at home and abroad.
The performance of positive electrode is most important to the raising of performance of lithium ion battery in lithium ion battery.Spinel-type mangaic acid Lithium (LiMn2O4) positive electrode is more mature one of anode material for lithium-ion batteries at present, there is such as promoter manganese to enrich, Technology of preparing is mature, production cost is low, has a safety feature and the advantages that no pollution to the environment.Especially in recent years, country is big Power develops the strategic new industry such as new energy and new-energy automobile, this is the scale business of lithium manganate having spinel structure positive electrode Using providing good opportunity.If the material is widely used as anode material for lithium-ion batteries, new one will be made greater efforts to promote For the research and development of high-performance, low cost and environment-friendly type power lithium-ion battery, and then promote New-energy electric vehicle industry Fast development.However, the positive electrode high temperature circulation stability is poor, the development of the lithium ion battery is seriously limited.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of lithium ion battery nucleocapsid positive electrode and preparation method thereof, Nucleocapsid positive electrode provided by the invention has excellent high temperature circulation stability.
To achieve the goals above, the present invention provides the following technical solutions：
The present invention provides a kind of lithium ion battery nucleocapsid positive electrodes, including chemical composition is LiMn2-xMxO4Nucleome And Li2MO3Shell；0 x≤0.1 <, the M are Si, Zr or Ti, and the valence state of M is positive tetravalence.
Preferably, the mass ratio of the nucleome and shell is 1：(0~x).
The present invention also provides a kind of preparation methods of lithium ion battery nucleocapsid positive electrode, include the following steps：
(1) mixed powder including lithium source, manganese source and doped source is provided；
The molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,0.1]；
(2) mixed powder that the step (1) obtains successively is pre-sintered and is re-sintered, obtain LiMn2-xMxO4Core Body；The temperature of the pre-sintering is 400~450 DEG C, and the time of pre-sintering is 4~6h；The temperature re-sintered be 750~ 825 DEG C, the time re-sintered is 12~18h；
(3) LiMn for obtaining the step (2)2-xMxO4Nucleome is mixed with dehydrated alcohol, deionized water, obtains nucleome point Dispersion liquid；
(4) it after mixing the step (3) obtained nucleome dispersion liquid and the alcoholic solution of doped source, is added dropwise into mixed liquor Ammonium hydroxide obtains sediment；
(5) sediment that the step (4) obtains is mixed with lithium source, carries out high temperature sintering, obtains lithium ion battery core Shell positive electrode Li2MO3@LiMn2-xMxO4；The temperature of the high temperature sintering is 700~900 DEG C, time of high temperature sintering is 3~ 10h；
Doped source independently includes silicon source, zirconium source or titanium source in the step (1) and step (4)；.
Preferably, the silicon source is ethyl orthosilicate；
The zirconium source is tetrabutyl zirconate；
The titanium source is butyl titanate.
Preferably, in the step (4) in amount≤step (1) of the substance of doped source the substance of doped source amount, doping The amount in source is with the meter of doped chemical；
The amount of the substance of lithium source is 2.1 times of the amount of doped source substance in step (4), the amount of lithium source in the step (5) With the meter of elemental lithium.
Preferably, the lithium source includes one of lithium carbonate, lithium hydroxide and lithium acetate or a variety of.
Preferably, the manganese source include manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, hydroxyl manganese oxide, manganese acetate, One of manganese carbonate, manganese nitrate and manganese oxalate are a variety of.
Preferably, the temperature being pre-sintered in the step (2) and the temperature re-sintered and the step (5) high temperature are burnt The temperature of knot is reached in a manner of heating, and the rate of the heating is independently 3~6 DEG C/min.
Preferably, in the step (4) ammonium hydroxide dosage so that mixed liquor pH value be 5~8.
Preferably, the preparation method of mixed powder includes in the step (1)：By lithium source, manganese source and doped source anhydrous It is dry after progress 3~8h of wet ball grinding in ethyl alcohol, obtain drying composite；The drying composite is subjected to dry grinding, is obtained To mixed powder.
The present invention provides a kind of lithium ion battery nucleocapsid positive electrodes, including chemical composition is LiMn2-xMxO4Nucleome And Li2MO3Shell；0 x≤0.1 <, the M are Si, Zr or Ti, and the valence state of the M is positive tetravalence.
In nucleocapsid positive electrode provided by the invention, in traditional positive electrode LiMn2O4In core adulterate high-valence state silicon, titanium or Zirconium, with LiMn2-xMxO4As nucleome, Mn in conventional lower valency doping vario-property is avoided3+The reduction of ion, and oxygen is inhibited to lack It falls into, while improving the diffusivity of lithium ion to a certain extent；Shell Li2MO3As Shell Materials, nucleome is coated, It realizes the isolation to nucleome active material and electrolyte, the direct contact of the two can be reduced, to restrained effectively nucleome The dissolution of middle manganese in the electrolytic solution, while the diffusivity of lithium ion is further improved, and then can show higher reversible Specific capacity and excellent cyclical stability, high rate performance and high temperature circulation stability；High temperature circulation stability of the present invention is excellent The different structural stability for being primarily due to doping vario-property in one side nucleome and improving material, another aspect shell lithium ion conductor Corrosion of the electrolyte to active material can be completely cut off, further increase the structural stability of material, in this way, electrochemistry charge and discharge Material can show preferable cycle performance in electric process.
Embodiment the result shows that, lithium ion battery nucleocapsid positive electrode provided by the invention recycles 100 under the conditions of 55 DEG C Capacity retention ratio is up to 95.1% after secondary.
Detailed description of the invention
Fig. 1 is Li prepared by the embodiment of the present invention 12SiO3@LiMn1.95Si0.05O4Process flow chart；
Fig. 2 is Li prepared by the embodiment of the present invention 12SiO3@LiMn1.95Si0.05O4High temperature cyclic performance figure in 0.5C.
Specific embodiment
The present invention provides a kind of lithium ion battery nucleocapsid positive electrodes, including chemical composition is LiMn2-xMxO4Nucleome And Li2MO3Shell.In the present invention, 0 x≤0.1 < in the nucleocapsid positive electrode, the x is more preferably 0.02~ 0.05；The M is Si, Zr or Ti.In the present invention, the mass ratio of the nucleome and shell is preferably 1：(0~x), further Preferably 1：(0.01~x).
In the present invention, the LiMn2-xMxO4The valence state of M is positive tetravalence in nucleome, realizes to conventional lithium ion anode Material LiMn2O4High-valence state doping vario-property.
The present invention also provides a kind of preparation methods of lithium ion battery nucleocapsid positive electrode, include the following steps：
(1) mixed powder including lithium source, manganese source and doped source is provided；
The molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,0.1]；
(2) mixed powder that the step (1) obtains successively is pre-sintered and is re-sintered, obtain LiMn2-xMxO4Core Body；The temperature of the pre-sintering is 400~450 DEG C, and the time of pre-sintering is 4~6h；The temperature re-sintered be 750~ 825 DEG C, the time re-sintered is 12~18h；
(3) LiMn for obtaining the step (2)2-xMxO4Nucleome is mixed with dehydrated alcohol, deionized water, obtains nucleome point Dispersion liquid；
(4) it after mixing the step (3) obtained nucleome dispersion liquid and the alcoholic solution of doped source, is added dropwise into mixed liquor Ammonium hydroxide obtains sediment；
(5) sediment that the step (4) obtains is mixed with lithium source, carries out high temperature sintering, obtains lithium ion battery core Shell positive electrode Li2MO3@LiMn2-xMxO4；The temperature of the high temperature sintering is 700~900 DEG C, time of high temperature sintering is 3~ 10h；
Doped source includes silicon source, zirconium source or titanium source in the step (1) and step (4).
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
The present invention provides the mixed powder including lithium source, manganese source and doped source.In the present invention, the lithium source preferably includes One of lithium carbonate, lithium hydroxide and lithium acetate are a variety of；The manganese source preferably includes manganese dioxide, manganese sesquioxide managnic oxide, four One of Mn 3 O, hydroxyl manganese oxide, manganese acetate, manganese carbonate, manganese nitrate and manganese oxalate are a variety of.In the present invention, institute Stating doped source includes silicon source, titanium source or zirconium source.In the present invention, the silicon source is preferably ethyl orthosilicate；The zirconium source is preferred For tetrabutyl zirconate；The titanium source is preferably butyl titanate.
In the present invention, the molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0, 0.1], further preferably 1：1.95~1.98：0.02~0.05；The dosage of the lithium source, manganese source and doped source is respectively to contain The meter of some elemental lithiums, manganese element and doped chemical.
In the present invention, the preparation method of the mixed powder preferably includes：By lithium source, manganese source and doped source in anhydrous second It is dry after progress 3~8h of wet ball grinding in alcohol, obtain drying composite；The drying composite is subjected to dry grinding, is obtained Mixed powder.
Lithium source, manganese source and doped source are preferably carried out drying after 3~8h of wet ball grinding by the present invention in dehydrated alcohol, are obtained Drying composite.In the present invention, the component of the lithium source, manganese source and doped source and dosage are consistent with preceding solution, This is repeated no more.In the present invention, the dosage of the dehydrated alcohol is to be able to achieve dividing for lithium source, silicon source and doped source mixture It dissipates, so that wet ball grinding is normally carried out.In the present invention, the time of the wet ball grinding is preferably 3~8h, further excellent It is selected as 5~6h；The wet ball grinding is sufficiently mixed lithium source, manganese source and doped source.Tool of the present invention to the wet ball grinding Body embodiment does not have particular/special requirement, using well-known to those skilled in the art.
After wet ball grinding, preferably wet ball grinding feed liquid is dried by the present invention, obtains drying composite.The present invention is to institute Stating dry specific embodiment does not have particular/special requirement, using the drying mode of ball milling feed liquid well-known to those skilled in the art ?.
After obtaining drying composite, the drying composite is preferably carried out dry grinding by the present invention, obtains mixed powder. The present invention does not have particular/special requirement to the specific embodiment of the dry grinding, using grinding well-known to those skilled in the art Mode.
After obtaining mixed powder, the mixed powder is successively pre-sintered and is re-sintered by the present invention, obtains LiMn2- xMxO4Nucleome.In the present invention, the temperature of the pre-sintering is 400~450 DEG C, preferably 420~425 DEG C；The pre-sintering Time be 4~6h, preferably 4.5~5h.In the present invention, the temperature of the pre-sintering is preferably reached in a manner of heating, The rate of the heating is preferably 3~6 DEG C/min, further preferably 4~5.5 DEG C/min.
In the present invention, the temperature re-sintered be 750~825 DEG C, preferably 770~820 DEG C, further preferably 780~800 DEG C；The time re-sintered is 12~18h, preferably 13~16h, further preferably 14~15h.In this hair In bright, the temperature re-sintered preferably is heated up to obtain by the temperature being pre-sintered；The rate of the heating is preferably 3~6 DEG C/ Min, further preferably 4~5 DEG C/min.The present invention can be tied using the step sintering mode re-sintered after being pre-sintered The LiMn that brilliant degree is good, partial size is more uniform2-xMxO4Nucleome；The M is Si, Zr or Ti, and the valence state of M is positive tetravalence.
Obtain LiMn2-xMxO4After nucleome, the present invention is by the LiMn2-xMxO4Nucleome and dehydrated alcohol, deionized water are mixed It closes, obtains nucleome dispersion liquid.The present invention does not have particular/special requirement to the dosage of the dehydrated alcohol, deionized water, to be able to achieve pair LiMn2-xMxO4Nucleome is sufficiently mixed.The present invention does not have particular/special requirement to the hybrid mode, using those skilled in the art institute Well known mode.
After obtaining nucleome dispersion liquid, after the present invention mixes the nucleome dispersion liquid and the alcoholic solution of doped source, to mixing Ammonium hydroxide is added dropwise in liquid, obtains sediment.In the present invention, the dosage of the doped source for mixing with nucleome dispersion liquid is with nuclear regime During standby on the basis of the dosage of doped source, with the meter of doped chemical in doped source, for what is mixed with nucleome dispersion liquid The amount of the substance of doped source during amount≤nuclear regime of the substance of doped source is standby.In the present invention, the doped source with it is aforementioned Technical solution LiMn2-xMxO4Doped source is consistent during nuclear regime is standby, and details are not described herein.In the present invention, the doped source Alcoholic solution in solvent be preferably dehydrated alcohol；The present invention does not have particular/special requirement to the dosage of the solvent, can to adulterate It sufficiently dissolves in source.
The present invention does not have particular/special requirement to the hybrid mode of the alcoholic solution of the nucleome dispersion liquid and doped source, using ability The hybrid mode of solution known to field technique personnel.After the mixing, ammonium hydroxide is added dropwise into mixed liquor by the present invention, obtains Sediment.Red in the present invention, the dosage of the ammonium hydroxide is so that the pH value of mixed liquor is subject to 5~8.The present invention is to mixed liquor Middle dropwise addition ammonium hydroxide, so that doped source forms the corresponding oxide of doped chemical in core surface.
It completes after being added dropwise, solid product is preferably washed and dried by the present invention, obtains dry sediment.The present invention There is no particular/special requirement to the washing and dry specific embodiment, is washed using material well-known to those skilled in the art With drying mode.
After obtaining sediment, the present invention mixes the sediment with lithium source, carries out high temperature sintering, obtains lithium ion battery Nucleocapsid positive electrode Li2MO3@LiMn2-xMxO4.In the present invention, the lithium source preferably includes lithium carbonate, lithium hydroxide and acetic acid One of lithium is a variety of.In the present invention, the dosage of the lithium source is with the use of the doped source for mixing with nucleome dispersion liquid Meter, the amount of the substance of the lithium source are 2.0~2.1 times of the amount of doped source substance, and the amount of the lithium source is mixed in terms of elemental lithium The amount in miscellaneous source is with the content meter of doped chemical.
Sediment and the mixture of lithium source are carried out high temperature sintering by the present invention, obtain lithium ion battery nucleocapsid positive electrode. In the present invention, the temperature of the high temperature sintering be 700~900 DEG C, preferably 750~850 DEG C, further preferably 780~ 800℃；The time of the high temperature sintering is 3~10h, preferably 4~6h.In the present invention, the temperature of the high temperature sintering is excellent Choosing is reached in a manner of heating up；The rate of the heating is preferably 3~6 DEG C/min, further preferably 3.5~5 DEG C/min.This Invention is changed into Li in the high-temperature sintering process, in the oxide of core surface2MO3Shell is coated on core surface.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to lithium ion battery nucleocapsid provided by the invention Positive electrode and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Lithium ion battery nucleocapsid positive electrode is prepared according to flow chart shown in FIG. 1：By lithium carbonate, mangano-manganic oxide and The ethanol solution of ethyl orthosilicate is 1.05 according to the molar ratio of Li, Mn and Si：1.95：0.05 mixing, and wet ball grinding 3 Hour.After to ball milling, obtained mixed slurry is transferred in evaporating dish and is dried.Finally, by dry mixture Grinding is uniformly placed on 450 DEG C pre-burning 4 hours in Muffle furnace, and regrinding is placed in Muffle furnace burns 18 hours i.e. for 800 DEG C eventually Obtain LiMn1.95Si0.05O4。
By the LiMn of 10g1.95Si0.05O4Ultrasonic disperse is in appropriate dehydrated alcohol and the mixed solution of deionized water, then 0.16g ethyl orthosilicate is dissolved in dehydrated alcohol, then the mixing of the ethanol solution of ethyl orthosilicate and nucleome is molten After liquid mixing, ammonium hydroxide is added dropwise, generates precipitating.By the washing of obtained sediment it is dry after and the lithium nitrate (substance of lithium in lithium nitrate Amount be 2.1 times of amount for coating silicon matter in shell ethyl orthosilicate) be uniformly mixed, be placed in 750 DEG C of hot environment High-temperature roasting 6h obtains manganate cathode material for lithium Li2SiO3@LiMn1.95Si0.05O4, wherein shell Li2SiO3Quality is LiMn1.95Si0.05O4The 5% of nucleome quality.
To manganate cathode material for lithium manufactured in the present embodiment and conventional cathode material LiMn2O4Carry out constant current charge-discharge Test.According to test result, composite positive pole specific discharge capacity with higher, excellent stable circulation performance, big times Rate performance and high-temperature behavior.Under 55 DEG C of hot environments, when charge-discharge magnification is 0.5C, the composite positive pole is for the first time Specific discharge capacity can reach 133.5mAh/g, still can reach 124.7mAh/g after circulation 100 times, capacity retention ratio is up to 93.4%；High temperature cyclic performance curve graph of the two under the conditions of 0.5C as shown in Fig. 2, as shown in Figure 2, what the present embodiment obtained Positive electrode has more excellent high temperature circulation stability.
Embodiment 2：
By the ethanol solution of lithium hydroxide, electrolytic manganese dioxide and butyl titanate according to mole of Li, Mn and Ti Than being 1.05：1.95：0.05 mixing, and wet ball grinding 3 hours.After to ball milling, obtained mixed slurry is transferred to steaming It is dried in hair ware.Finally, dry mixture grinding is uniformly placed on 400 DEG C pre-burning 6 hours in Muffle furnace, grind again Mill is placed on 780 DEG C of whole burn 15 hours in Muffle furnace and obtains LiMn1.95Ti0.05O4。
By the LiMn of 10g1.95Ti0.05O4Then ultrasonic disperse adds in dehydrated alcohol and the mixed solution of deionized water 1.55g butyl titanate is dissolved in dehydrated alcohol, then by the mixed solution of the ethanol solution of the butyl titanate and nucleome After mixing, ammonium hydroxide is added dropwise, generates precipitating.(amount of the substance of lithium will be controlled with lithium hydroxide after the washing drying of obtained sediment It is 2.1 times of the amount of silicon matter in cladding shell) it is uniformly mixed, it is placed in 780 DEG C of hot environment high temperature roasting 4h, obtains manganese Sour lithium anode material Li2TiO3@LiMn1.95Ti0.05O4, wherein shell Li2TiO3Quality is LiMn1.95Ti0.05O4Nucleome quality 5%.
Constant current charge-discharge test is carried out to the manganate cathode material for lithium of preparation.According to test result, the anode composite material Expect specific discharge capacity with higher, excellent stable circulation performance, big high rate performance and high-temperature behavior.In 55 DEG C of high temperature rings Under border, when charge-discharge magnification is 0.5C, the first discharge specific capacity of the composite positive pole can reach 133.2mAh/g, circulation Still it can reach 126.7mAh/g after 100 times, capacity retention ratio is up to 95.1%.
Embodiment 3：
By the ethanol solution of lithium acetate, manganese sesquioxide managnic oxide and tetrabutyl zirconate according to the molar ratio of Li, Mn and Zr It is 1.05：1.95：0.05 mixing, and wet ball grinding 3 hours.After to ball milling, obtained mixed slurry is transferred to evaporation It is dried in ware.Finally, dry mixture grinding is uniformly placed on 400 DEG C pre-burning 6 hours in Muffle furnace, regrind It is placed on 780 DEG C of whole burn 15 hours in Muffle furnace and obtains LiMn1.95Zr0.05O4。
By the LiMn of 10g1.95Zi0.05O4Then ultrasonic disperse adds in dehydrated alcohol and the mixed solution of deionized water Simultaneously ammonium hydroxide is added dropwise in the ethanol solution of the tetrabutyl zirconate of 1.25g, generates precipitating.By the washing of obtained sediment it is dry after and Lithium acetate (amount of the substance of control lithium is 2.0 times for coating the amount of silicon matter in shell) is uniformly mixed, and is placed in 780 DEG C of high temperature Environment high temperature roasts 4h, obtains manganate cathode material for lithium Li2ZiO3@LiMn1.95Zi0.05O4, wherein shell Li2ZiO3Quality For LiMn1.95Zi0.05O4The 5% of nucleome quality.
Constant current charge-discharge test is carried out to the manganate cathode material for lithium of preparation.According to test result, the anode composite material Expect specific discharge capacity with higher, excellent stable circulation performance, big high rate performance and high-temperature behavior.In 55 DEG C of high temperature rings Under border, when charge-discharge magnification is 0.5C, the first discharge specific capacity of the composite positive pole can reach 133.0mAh/g, circulation Still it can reach 126.1mAh/g after 100 times, capacity retention ratio is up to 94.8%.
As seen from the above embodiment, Li provided by the invention2MO3@LiMn2-xMxO4It is specific discharge capacity with higher, excellent Different stable circulation performance, high rate performance and high-temperature behavior；The present invention uses high-valence state element doping and high-valence state element pair It answers the technique of lithium ion conductor cladding collaboration optimization to be modified lithium manganate having spinel structure, not only avoids conventional lower valency and mix Mn in miscellaneous modification3+The reduction of ion, and oxygen defect is inhibited, while improving the diffusivity of lithium ion to a certain extent, and And shell Li2MO3It restrained effectively the dissolution of manganese in electrolyte to the clad of nucleome, while further improving lithium ion Diffusivity.
Reaction raw material sources used in preparation process of the present invention are abundant, and inexpensively, production cost is low for price, is easy to Scale business application.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention, Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these Embodiment belongs to the scope of the present invention.

Claims (10)

1. a kind of lithium ion battery nucleocapsid positive electrode, including chemical composition are LiMn2-xMxO4Nucleome and Li2MO3Shell；0 < X≤0.1, the M are Si, Zr or Ti, and the valence state of M is positive tetravalence.
2. lithium ion battery nucleocapsid positive electrode according to claim 1, which is characterized in that the matter of the nucleome and shell Amount is than being 1：(0~x).
3. a kind of preparation method of lithium ion battery nucleocapsid positive electrode, includes the following steps：
(1) mixed powder including lithium source, manganese source and doped source is provided；
The molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,0.1]；
(2) mixed powder that the step (1) obtains successively is pre-sintered and is re-sintered, obtain LiMn2-xMxO4Nucleome；Institute The temperature for stating pre-sintering is 400~450 DEG C, and the time of pre-sintering is 4~6h；The temperature re-sintered is 750~825 DEG C, The time re-sintered is 12~18h；
(3) LiMn for obtaining the step (2)2-xMxO4Nucleome is mixed with dehydrated alcohol, deionized water, obtains nucleome dispersion Liquid；
(4) after mixing the step (3) obtained nucleome dispersion liquid and the alcoholic solution of doped source, ammonia is added dropwise into mixed liquor Water obtains sediment；
(5) sediment that the step (4) obtains is mixed with lithium source, carries out high temperature sintering, is obtaining lithium ion battery nucleocapsid just Pole material Li2MO3@LiMn2-xMxO4；The temperature of the high temperature sintering is 700~900 DEG C, and the time of high temperature sintering is 3~10h；
Doped source independently includes silicon source, zirconium source or titanium source in the step (1) and step (4)；
The M is Si, Zr or Ti.
4. preparation method according to claim 3, which is characterized in that the silicon source is ethyl orthosilicate；
The zirconium source is tetrabutyl zirconate；
The titanium source is butyl titanate.
5. preparation method according to claim 3, which is characterized in that the amount of the substance of doped source in the step (4)≤ The amount of the substance of doped source in step (1), the amount of doped source is with the meter of doped chemical；
The amount of the substance of lithium source is 2.0~2.1 times of the amount of doped source substance in step (4), the amount of lithium source in the step (5) With the meter of elemental lithium.
6. preparation method according to claim 3, which is characterized in that the lithium source includes lithium carbonate, lithium hydroxide and second One of sour lithium is a variety of.
7. preparation method according to claim 3, which is characterized in that the manganese source include manganese dioxide, manganese sesquioxide managnic oxide, One of mangano-manganic oxide, hydroxyl manganese oxide, manganese acetate, manganese carbonate, manganese nitrate and manganese oxalate are a variety of.
8. preparation method according to claim 3, which is characterized in that the temperature that is pre-sintered in the step (2) and reburn The temperature of knot and the temperature of the step (5) high temperature sintering are reached in a manner of heating, and the rate of the heating is independent It is 3~6 DEG C/min.
9. preparation method according to claim 3, which is characterized in that the dosage of ammonium hydroxide is so that mixed in the step (4) The pH value for closing feed liquid is 5~8.
10. preparation method according to claim 3, which is characterized in that the preparation method of mixed powder in the step (1) Including：It is dried after lithium source, manganese source and doped source to be carried out to 3~8h of wet ball grinding in dehydrated alcohol, obtains drying composite；It will The drying composite carries out dry grinding, obtains mixed powder.
CN201810745388.6A 2018-07-09 2018-07-09 A kind of lithium ion battery nucleocapsid positive electrode and preparation method thereof Pending CN108899523A (en)

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Application publication date: 20181127