CN105118983B - Method for preparing lithium nickel manganese oxide anode material - Google Patents

Method for preparing lithium nickel manganese oxide anode material Download PDF

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Publication number
CN105118983B
CN105118983B CN201510480823.3A CN201510480823A CN105118983B CN 105118983 B CN105118983 B CN 105118983B CN 201510480823 A CN201510480823 A CN 201510480823A CN 105118983 B CN105118983 B CN 105118983B
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nickel
lithium
manganese
cathode material
lithium manganate
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CN105118983A (en
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杨静
陈莎
王祖静
蔡爽
林定文
胡辉
丁先红
舒方君
张文博
周环波
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Hubei Uee Energy Technology Co Ltd
Hubei Engineering University
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Hubei Uee Energy Technology Co Ltd
Hubei Engineering University
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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
    • H01M4/48—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for preparing a lithium nickel manganese oxide anode material. The method includes the steps that A, divalent nickel salt, divalent manganese salt and Li＜+＞ compounds are evenly mixed and grinded, and a nickel, manganese and lithium mixture is obtained; B, persulfate with the molar weight larger than the sum of the molar weight of the divalent nickel salt and the molar weight of the divalent manganese salt and the mixture obtained in the step A are mixed and grinded, and a reaction mixture is obtained; C, the reaction mixture obtained in the step B is transferred into a polytetrafluoroethylene reaction kettle, water is added, a cover and a stainless steel reaction-kettle outer bush are arranged for sealing, the reaction temperature is controlled and kept, and reactants are obtained; D, the reactants obtained in the step C are taken out and washed with water till no sulfate radical is detected, suction filtration is carried out, and brown or black solid is obtained; E, the brown or black solid is transferred into a crucible, in the atmosphere environment, roasting is carried out, natural cooling is carried out, and the lithium nickel manganese oxide anode material is obtained. The raw materials are abundant, the price is low, environment pollution is avoided, and a brand new easy and convenient solid-liquid film phase reaction method with the easily-controlled conditions and the simple devices is adopted.

Description

A kind of preparation method of nickel lithium manganate cathode material
Technical field
The present invention relates to battery material technical field, is more particularly to a kind of preparation method of nickel lithium manganate cathode material.
Background technology
Existing most widely used lithium rechargeable battery, its positive active material is mostly LiCoO2、LiMn2O4、 LiNiO2Deng compound, or the compound of the mutual doping vario-property based on three kinds of compounds, i.e., so-called binary material (such as LiNixMn2-xO4、LiCoxMn2-xO4、LiNixCo1-xO2、LiNi0.5Mn1.5O4Deng) or ternary material (such as LiNixCoyMn2-x- yO4、LiNi1/3Co1/3Mn1/3O2Deng) for lithium ion battery positive active material；Or with LiFePO4For positive active material. Various compounds all have respective advantage and deficiency as anode material for lithium-ion batteries.The method for synthesizing these materials is main There are liquid phase reactor method, the big class of solid reaction process two.Wherein liquid phase method includes coprecipitation, sol-gel process, microemulsion method, heat Liquid (or hydro-thermal) method and Rheological Phase Method synthetic technology etc..Solid reaction process is by solid reactant, under the high temperature conditions instead Should, corresponding active material is generated (such as document：Lithium ion anode material LiMn2O4 doping vario-property studies [J], inorganic salt worker Industry, 2012,44 (6)：61-62).Solid phase reaction reaction temperature height (generally between 500~900 DEG C, even as high as 1000 DEG C (such as document：Novel synthesis and electrochemical behavior of layered LiNi0.5Mn0.5O2 [J], J.Alloys and Compounds, 2008,449：296–299.Combustion-synthesized LiNi0.6Mn0.2Co0.2O2As cathode material for lithium ion batteries [J], J.Alloys and Compounds, 2014,609：143-149), reaction time length is (generally in 24~36h and the above even more up to a couple of days (such as text Offer：Sintering temperature studies [J] to LiMn2O4 structure and Electrochemical Performances, inorganic chemicals industry, and 2012,44 (7)：31-46). And so-called coprecipitation, typically all with the predecessor of Co deposited synthesis active material, then with predecessor as raw material, Jing solid phases Battery positive electrode active material is synthesized (such as document：NEW TYPE OF COMPOSITE coprecipitation prepares the secondary electricity of high-energy/high-power lithium ion Pond 5V positive electrode LiNi0.5Mn1.5O4And its chemical property [J], Acta PhySico-Chimica Sinica, 2014,30 (4)：669-676.A high-powered concentration-gradient Li(Ni0.85Co0.12Mn0.03)O2cathode material for Lithium ion batteries [J], J.Power Sources, 2014,263：203-208.Co-precipitation synthesis of Ni0.6Co0.2Mn0.2(OH)2precursor and characterization of LiNi0.6Co0.2Mn0.2O2Cathode material for secondary lithium batteries [J], Electrochimica Acta.2014,130:The rich lithium of 82-89. wet chemistry methods synthesis and mix aluminate type LiMn2O4 and its The improvement [J] of electrical property, Journal of Inorganic Materials, 2013,28 (3)：337-340), then by coprecipitation the predecessor for obtaining passes through Solid phase reaction, obtains end product, it is clear that not only synthesis technique is more complicated for such method, similarly being total to solid phase reaction Same defect.Although the positive electrode of the small Nano grade of sol-gel process energy synthesis particle, also can only first close Into predecessor, then through high temperature solid state reaction will sol-gel process synthesis predecessor roasting, may also need subsequently to be located Reason, finally can just obtain target product.Sol-gel method craft flow process is not only very numerous and diverse, and technological parameter is also very difficult Strictly to control (such as document：Li1.2Mn0.54Co0.13Ni0.13O2@V2O5The preparation of core-shell composite material and its chemical property [J], Journal of Inorganic Materials, 2014,29 (3)：257-263；Anode material for lithium-ion batteries Li (Ni, Co, Mn) O2Research enter Exhibition [J], new chemical materialses, 2014,42 (7)：21-23), also relatively it is difficult to the industrialized production of lithium ion anode material.It is micro- Emulsion method is by the use of organic matter as solvent, with the coprecipitation that water is mixed to form microemulsion, it is clear that the method building-up process will Use many organic compounds, including organic solvent, organic surface active agent, organic matter auxiliary agent etc., also can only synthesizing lithium ion The predecessor of positive electrode or negative material is (such as document：A new form of manganese carbonate for the Negative electrode of lithium-ion batteries [J], J.Power Sources, 2011,196：2863- 2866；Surfactant-assisted microemulsion approach of chrysanthemum-like Co3O4Microspheres and their application in lithium-ion battery [J], Solid State Ionics, 2013,231：63–68.)；Document " LiNi1/3Co1/3Mn1/3O2-Graphene Composite as a Promising Cathode Lithium-Ion Batteries[J]”(ACS Appl.Mater.Interfaces,2011,3: 2966-2972) a kind of microemulsion method is described, LiNi is prepared1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Mn1/3O2- Graphene positive pole The method of material, preparation process is likely to cause bad impact to environment, and preparation technology flow process is also more numerous and diverse, it is difficult to realize The scale industrial production of material.Traditional hydro-thermal method or referred to as hydrothermal method typically use certain density reactant solution, in Sealing state in reactor, in a certain temperature conditions (usually 50~200 DEG C) reaction regular hour (usually 12h Or more than 24h even a couple of days), prepare predecessor.Document " Nanostructured Hybrid Layered-Spinel Cathode Material Synthesized by Hydrothermal Method for Lithium-Ion Batteries [J] " (ACS Appl.Mater.Interfaces, 2014,6：8363-8368) describe a kind of hydrothermal process, synthesis stratiform- Spinelle and spinel-type lithium-ion cell positive material Li2MnO3-LiNi0.5Mn1.5O2、LiNi0.5Mn1.5O4.Specific method It is：By 2.685g solid LiOHH2O is dissolved in wiring solution-forming in 25mL deionized waters, then under agitation, is slowly added dropwise To the MnSO containing 1.01g4·H2The NiSO of O, 0.525g4·6H2(the NH of O and 1.36g4)2S2O8In the aqueous solution, then shift To in the reactor of sealing, react 1~24 hour under the conditions of 180 DEG C, be then dried by strong stirring, finally existed Roasting 8h is obtained at 800 DEG C.Document " One-step hydrothermal method synthesis of core-shell LiNi0.5Mn1.5O4Spinel cathodes for Li-ion batteries [J] " (J.Power Sources, 2014,256 (15)：66-70) also describe a kind of hydrothermal method and prepare core-shell structure, the LiNi of powder dress0.5Mn1.5O4The side of positive electrode Method.Its typical method is：The NiSO of 12.5mmol (mM, as follows)4·6H2The MnSO of O, 37.5mmol4·H2O with The urea of 0.1mol is dissolved in wiring solution-forming in the deionized water of 25mL, in being then transferred into ptfe autoclave, sealing, 180 DEG C of insulation 12h, naturally cool to room temperature, through series of processes, obtain Ni0.5Mn1.5CO3Predecessor, then through deionized water The removal of impurity is gone for several times in washing, then is pre-processed 3 hours through 500 DEG C, afterwards with the LiOHH of corresponding chemical metered mass2O is mixed Close, the roasting at 850 DEG C is that solid state reaction kinetics prepare target positive electrode LiNi0.5Mn1.5O4." prepared by hydro-thermal method for document LiNi0.5Mn1.5O4And its research [J] of chemical property " (Jilin Institute of Chemical Technology journal, 2014,31 (1):95-100) introduce A kind of LiNi0.5Mn1.5O4The hydrothermal preparing process of material.Its concrete grammar and process are：Compound concentration be 0.159, 0.162、0.165、0.169g·mL-1The each 15mL of LiOH solution, solution is dropwisely added and fills 0.0075 mole of MnSO4· H2O, 0.0025 mole of NiSO4·H2O, 0.0075 mole of (NH4)2S2O8Inner liner of reaction kettle in, in placing into air dry oven Constant temperature 24h, suction filtration at 180 DEG C, are put in constant temperature 24h at 120 DEG C of air dry oven and obtain sample being precipitated, then obtaining Sample be placed in tube furnace under air atmosphere, 850 DEG C of constant temperature are heat-treated 24h, obtain positive electrode.Document " reduction hydrazine hydrate To LiNi0.5Mn1.5O4The impact [J] of structure and performance " (functional material, 2013,44 (11)：1535-1542) also describe one Plant hydro-thermal method and prepare LiNi0.5Mn1.5O4The technology of positive electrode, specifically：50 DEG C, under stirring condition, to containing certain hydrazine hydrate NaOH solution solution in, add mol ratio be 1:3 NiSO4And MnSO4It is synthesized solid precursors, then by predecessor With LiOHH2O mixes, Jing solid phase reactions (600 DEG C, 850 DEG C at roasting 24h) and obtain LiNi0.5Mn1.5O4Material.
Rheological Phase Method synthetic technology because preparation process is simple, environmental protection, product grain fine uniform and have more correlation Particular technique disclose.The specific practice of rheology phase synthesi is：Two kinds or two or more solid reactants machinery are mixed Close after uniform grinding plus appropriate water or other solvents, be modulated into rheology state, under rheology state, solid mixture and solvent are abundant Contact forms not stratified rheology system.By the system be placed in it is appropriate under conditions of reaction (heating or heating stirring be dried or Directly dry), precursors are obtained, then presoma is thermally decomposed to yield into sample and (referred to：Document " LiNi0.5Mn1.5O4/Ag The preparation of composite and chemical property [J] ", China YouSe Acta Metallurgica Sinica, 2010,20 (4):801-806 etc.).Document “LiNi0.5Mn1.5O4The preparation of/Ag composites and chemical property [J] " (China YouSe Acta Metallurgica Sinica, 2010,20 (4): 801-806) Rheological Phase Method of report prepares LiNi0.5Mn1.5O4/ Ag's comprises the concrete steps that：By CH3COOLi·2H2O (analysis is pure) 3.00g、Ni(NO3)2(analysis is pure) 2.68g and MnCO3(analysis is pure) 5.07g is fully ground, and adds a certain amount of ethanol+water (body Product is than being 1:1) solution, by mixture pasty state is transferred to, be subsequently adding the ammoniacal liquor of 10mL30%, be fully ground after be placed in 150 DEG C of bakings Dry in case, obtain predecessor, then presoma is processed into 4h decomposition acetate in 400 DEG C of air atmospheres, in 850 DEG C of heating 6h, most heats 12h (reoxidizing) after 600 DEG C, and cooling obtains LiNi0.5Mn1.5O4.Again plus AgNO3A series of process of Jing, finally Obtain LiNi0.5Mn1.5O4/ Ag composites.Document " anode material for lithium-ion batteries (LiNi1/3Co1/3Mn1/3O2) rheology phase Method synthesizes and its chemical property [J] " (synthesis chemistry, 2015,23 (3):191-193) describe a kind of LiNi1/3Co1/ 3Mn1/3O2The synthetic method of positive electrode, particularly：In 50mL deionized waters, addition Li, Ni, Co, Mn mol ratio is 1.04:1:1:1 lithium carbonate, nickel nitrate, cobalt sesquioxide and manganese dioxide, are stirred at room temperature 4h to rheology phase, and 90 DEG C to moisture Evaporating completely, grinding obtains predecessor powder, and predecessor powder is placed in 750 DEG C of calcining 8h of atmospheric atmosphere in Muffle furnace, is cooled to Room temperature, grinding obtains grey powder.Document " the spinelle LiNi of Rheological Phase Method synthesis ZnO claddings0.5Mn1.5O4[J] " (battery, 2010,40 (4):205-206), a kind of Rheological Phase Method synthesis LiNi is also reported0.5Mn1.5O4The technology of material, particularly： By LiNi0.5Mn1.5O4Stoichiometric proportion, by CH3COOLi、Ni(CH3COO)2、Mn(CH3COO)2Mixing, adds ethanol-distillation Water (volume ratio V/V=1:1) modulate to pasty state, add 30%NH3·H2O is dried 6h to rheology state at 150 DEG C, obtains forerunner Body, presoma is processed in Muffle furnace 4h at 400 DEG C, then 6h is heated at 850 DEG C, finally makes annealing treatment 8h at 600 DEG C, Along with the furnace cooling, obtains LiNi0.5Mn1.5O4.Document " 5V positive electrode LiNi0.5Mn1.5O4-xFx(x=0.01) Rheological Phase Method system It is standby with characterize [J] " (fine chemistry industry, 2010,2:112-116), document " the Rheological Phase Method synthesis of ethylene glycol solvent LiNi0.5Mn1.5O4The research of positive electrode " (Xinyu institute journal, 2013,18 (5):110-112), document " stratiform LiMnO2's Soft chemical method synthesis and the research of chemical property " (Wuhan University Journal (Edition), 2004,50 (2):165-168), document " Rheological Phase Method synthetic spinel type LixMn2O4And its chemical property " (Central South University's journal, 2002,33 (3):250-253)、 Document " the orthogonal LiMnO of Rheological Phase Method one-step synthesis2Structure and performance [J] " (Materials Science and Engineering journal, 2008,26 (1):35-38) etc., Rheological Phase Method is introduced respectively has synthesized LiNi0.5Mn1.5O4-xFx(x=0.01), LiNi0.5Mn1.5O4, stratiform LiMnO2, spinel-type LixMn2O4With orthogonal LiMnO2Deng synthetic technology, concrete grammar is approximate with above-mentioned literature method.This Outward, document " Structure and electrochemical behaviors of spherical Li1+xNi0.5Mn0.5O2+δ synthesized by rheological phase reaction method[J]”(Electrochimica Acta, 2014,150:89-98) describe a kind of Li1+xNi0.5Mn0.5O2+δThe rheology of positive electrode is combined to technology.Document “LiNi0.5Mn1.5O4spinel cathode using room temperature ionic liquid as electrolyte[J]”(Electrochimica Acta,2013,101:151-157.) disclose a kind of spinel-type positive pole Material LiNi0.5Mn1.5O4Method, the specific practice of the document is：By LiOH, Ni (CH3COO)2·4H2O、Mn (CH3COO)2·4H2O and citric acid are according to mol ratio=1:0.5:1.5:3.6 ratio mixing, adds appropriate water, modulation Into rheology phase, 90 DEG C of heating 12h obtain predecessor, and then predecessor 500 DEG C of heating 5h under air atmosphere, are warmed up to successively 680 DEG C, 750 DEG C and 820 DEG C are heated respectively 8h and obtain target product.Document " Electrochemical properties of LiNi0.5Mn1.3Ti0.2O4/Li4Ti5O12cells[J]”(International Journal of Minerals, Metallurgy and Materials,2012,199(5):457-460), document " Preparation and Electrochemical Properties of LiMn2O4by a Rheological-Phase-Assisted Microwave Synthesis Method[J]”(Inorganic Materials,2008,44(5):542-548), document " Rheological Phase Synthesis and Electrochemical Properties of Mg-Doped LiNi0.8Co0.2O2Cathode Materials for Lithium-Ion Battery[J])”(Journal of The Electrochemical Society,2008,155(7):) and document " Synthesis of layered- A520-A525 structure LiMn1-xCrxO2for lithium-ion batteries by the rheological phase method [J]”(Materials Letters,2004,58:1620-1624) etc., rheology is described respectively is combined to technology synthesis LiNi0.5Mn1.3Ti0.2O4/Li4Ti5O12、LiMn2O4, Mg- doping LiNi0.8Co0.2O2And LiMn1-xCrxO2Lithium ion battery The technology of positive electrode.Obviously, in addition to technical step is numerous and diverse, the modulation of rheology phase is likely to be subject to Rheological Phase Method synthetic technology The impact of many uncertain factors, thus randomness is stronger, the uniformity of the material comprehensive electrochemical of synthesis is possible to be lacked Lose.Therefore, rheology be combined to that technical step is numerous and diverse, synthesis cost may the high, uniformity of product be likely to poor, be also relatively difficult to Realize effective scale industrial production.
US No. 8,431,108 patents in the U.S. disclose a kind of nanometer LiMn2O4, nanometer LiNi0.5Mn1.5O4And nanometer LiNi0.5Mn1.5O4-δThe liquid phase preparation process of positive electrode and this different materials, particularly sol-gel process (i.e. Sol-gel Method) technology of preparing.US No. 9,054,379 patents in the U.S. disclose lithium ion battery composite cathode material AlPO4-LiCoO2、 AlPO4-LiNi0.5Mn1.5O4、AlPO4-LiNi1/3Co1/3Mn1/3O4Deng liquid phase preparation process.U.S. US 8,980,140 is specially Profit discloses Li4Ti5O12Based on, with alkali metal or alkaline-earth metal or the doping such as rare earth metal or lanthanide series metal or actinide metals Modified lithium ion battery composite cathode material Li(4-g)AgTi5O12、Li4AhTi(5-h)O12Deng liquid phase preparation process.U.S. US No. 8,968,669 patents are disclosed with ternary material LiNixMnyCozO2Based on, with K, Na, Cs, Rb, V, Cu, Al, Mg, Fe, Ti, Cr, Zr or C etc. modified lithium ion battery composite cathode material Lia(NixMnyCoz)MeObDeng liquid phase preparation process.
Chinese Patent Application No. 201410838921.5,201510045813.7 patents, individually disclose a kind of high temperature and consolidate Phase reaction synthesizes a kind of LiMn2O4The hydro-thermal method synthesis of/carbon nano tube compound material, a kind of hollow ball shape manganate cathode material for lithium Method.201510045813.7 the specific practice of the hydro-thermal method of patent is：First by potassium sulfate solution and persulfate aqueous solution After mixing, add the concentrated sulfuric acid to carry out hydro-thermal reaction, obtain hollow manganese dioxide ball, then mix with soluble lithium salt, it is ultrasonic at Reason, drying are calcined and obtained (refer to summary and specification).The patent of Chinese Patent Application No. 201410843002.7 discloses one Plant Co deposited synthesis Li1+xMn2-x-yAyQzO4(A=Al and/or Mg and/or Co；Q=Mg and/or Co and/or Nb and/or Cr Deng) method of material.The patent of Chinese Patent Application No. 201510012421.0 discloses a kind of Hydrothermal Synthesiss technology synthesis nanometer The method of high-purity lithium manganate material.Its specific practice (referring to the 1~embodiment of embodiment 5 of specification) is：Configuration reactant liquor in In the reactor of 40mL, reactant liquor contains a certain amount of potassium permanganate, ascorbic acid, lithium hydroxide, anti-at 160~200 DEG C Answer 5~8 hours, separation, drying to obtain nanometer lithium manganate.The patent of Chinese Patent Application No. 201510026386.8 discloses one Plant co-precipitation and combine solvent thermal technology (similar hydro-thermal method) synthesis nickel ion doped LiNi0.5Mn1.5O4The method of material.Specific side Method is：With cetyl trimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) as template, with urea as precipitating reagent, First Ni is synthesized with solvent thermal technology0.25Mn0.75CO3Predecessor, then through solid state reaction kinetics nickel ion doped LiNi0.5Mn1.5O4 The method of material.The patent of Chinese Patent Application No. 201510026729.0 discloses one kind and prepares modified nickel ion doped LiNi0.5Mn1.5O4The method of positive electrode.The patent of Chinese Patent Application No. 201510043316.3 discloses a kind of liquid phase reactor With reference to heat treatment solid phase reaction, Al is used2O3And ZrO2Etc. the method that is mixed with, modified lithium manganate LiMn is prepared2O4, nickel ion doped LiNi0.5Mn1.5O4The method of positive electrode.The patent of Chinese Patent Application No. 201510067722.3 discloses a kind of with common Cobalt acid lithium, lithium nickelate, LiMn2O4, nickel ion doped, LiFePO4, lithium manganese phosphate, ferric metasilicate lithium, fluorosulfuric acid ferrous lithium etc. are base Plinth, through solid phase reaction, then coats similar to matrix composition or identical corresponding clad, prepares the lithium of coating modification The method of ion battery positive electrode.The patent of Chinese Patent Application No. 201510071425.6 discloses a kind of aqueous sol-solidifying Glue (Sol-gel) method combines heat treatment (self-propagating combustion) solid phase reaction, prepares high potential lithium ion battery anode material nickel LiMn2O4 LiNi0.5Mn1.5O4Method.The patent of Chinese Patent Application No. 201510071733.9 discloses a kind of solid phase reaction, The method for preparing the modified lithium ion battery anode material nickel LiMn2O4 of strontium doping.
Relevant LiCoO disclosed in the above-mentioned document report of comprehensive analysis and Patents2、LiMn2O4、LiNiO2、LiFePO4、 LiNi0.5Mn1.5O4The synthesis of existing solid phase reaction, liquid phase reactor and Rheological Phase Method etc. various types of lithium ion anode materials Etc. synthetic technology, the open defect or deficiency of following aspect are primarily present：
First, solid state reaction kinetics LiNi0.5Mn1.5O4The material of poor, synthesis Deng anode material for lithium-ion batteries homogeneity Uniformity is bad, and easily to be mixed into, impurity, reaction speed be slow, the reaction time is long, and energy ezpenditure is high, the pattern of product, grain Footpath etc. is difficult to control to, and raw material types are limited seriously (to be typically only capable to the labile compound of appearance and will not produce the oxygen of impurity Compound, hydroxide and nitrate, acetate etc.), synthesize relatively costly, although can accomplish scale production, but be difficult to reality Now it is widely applied.
Second, microemulsion method synthesis LiNi0.5Mn1.5O4Deng anode material for lithium-ion batteries, substantial amounts of organic solvent is used, Substantial amounts of organic matter surfactant, has a certain impact to environment；The formation of microemulsion needs harsh condition, synthesis technique Step is various, and material manufacture is relatively costly, and is limited by method itself, it is more difficult to realize extensive efficiently production.
3rd, hydrothermal solution or hydro-thermal method LiNi0.5Mn1.5O4Deng anode material for lithium-ion batteries, although close without solid phase reaction Into technology and microemulsion reaction methods technology etc. reaction is uneven, reaction time length and seriously polluted, cost are high etc. not enough or scarce Fall into, but equally exist the defects such as harsh, the equipment technical requirements height of high energy consumption, process regulation, simultaneous reactions are in solution State is carried out, and because being limited by concentration, synthetic product amount is extremely limited, if solution concentration being significantly increased or increasing reaction Kettle is accumulated, then technical difficulty, the performance of the product such as LiNi of synthesis is significantly greatly increased0.5Mn1.5O4Deng structure, pattern, particle diameter with And the uncertainty of chemical property etc. is also significantly greatly increased.Hydro-thermal method synthesizes LiNi0.5Mn1.5O4Deng anode material for lithium-ion batteries Also technology is relatively difficult to efficient industrial-scale production.
The content of the invention
In order to solve above-mentioned the shortcomings of the prior art, the purpose of the present invention is to there are provided a kind of nickel manganese The preparation method of sour lithium anode material.The original that the method is polluted using abundant raw material, cheap, non-environmental-pollution or low environment Material, nickel ion doped is being prepared just with the new solid-liquid film phase reaction method that relatively simple, condition is easily controllable, equipment is relatively simple Pole material.
In order to realize above-mentioned purpose, the present invention is employed the following technical solutions：
A kind of preparation method of nickel lithium manganate cathode material, comprises the steps and process conditions：
The first step is by the divalent nickel salt of 0.02~0.33mol (mole, as follows) and the bivalent manganese of 0.06~1.0mol Salt, Li+Molal quantity be 0.65~12.5mol lithium compound mixed grinding it is uniform, obtain nickel, manganese, lithium mixture；
Second step is by persulfate that mole is 1.05~1.20 times of divalent nickel salt and manganous salt integral molar quantity and the Mixture mixed grinding described in one step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, is added 1~50mL water, is added Cover, add the sealing of stainless steel cauldron overcoat, 60~200 DEG C of controlling reaction temperature to be incubated 4~36 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with water to sulfate radical-free detection and (is dripped with saturation barium chloride As follows without muddy or precipitation in being added to eluate, omit), suction filtration, obtain brown or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, under 650~950 DEG C of atmospheric environments, roasting 4~12 Hour, naturally cool to room temperature, that is, obtain nickel lithium manganate cathode material.
A kind of described nickel lithium manganate cathode material is prepared from by said method.
In order to the present invention is better achieved, described divalent nickel salt includes：Nickel acetate (NiAc2·4H2O, wherein Ac=vinegar Acid group, i.e. CH3COO-, it is as follows), nickel nitrate [Ni (NO3)2·6H2O], nickel chloride (NiCl2·6H2) or nickel sulfate O (NiSO4·6H2O the one kind or two kinds to four kinds of equimolar mixture in)；
Described manganous salt includes：Manganese acetate (MnAc2·4H2O), manganese nitrate [Mn (NO3)2·6H2O], manganese chloride (MnCl2·4H2O), manganese sulfate (MnSO4·H2O)；Described lithium compound includes：Lithia (Li2O), lithium hydroxide (LiOH·H2O the one kind or two kinds to four kinds of equimolar mixture in)；
Described persulfate includes：Ammonium persulfate [(NH4)2S2O8], potassium peroxydisulfate (K2S2O8), sodium peroxydisulfate (Na2S2O8) etc. one kind therein；
Described water includes：The one kind therein such as distilled water, pure water, deionized water.
The present invention is a kind of brand new technical route of synthesis of anode material of lithium-ion battery, its reaction principle chemical reaction And solid-liquid film mutually illustrates formula to be expressed as follows：
xNi2++yMn2++(x+y)S2O8 2-+nH2O→NixMnyO2·nH2O(s)+(x+y)SO4 2-
(intermediate or reactive intermediate, black)
Li++NixMnyO2·nH2O(s)→LiNixMnyO4(s)+nH2O
(brown or black)
Wherein：X represents the molal quantity of Ni, and y represents the molal quantity of Mn.
Can be seen that because reactant feed is all soluble solid reagent, because adding in formula and Figure 13 from the reactions above The water yield for entering is less, can only dissolve the material of fraction solids reaction-ure surface, and forms saturated solution on reaction raw materials surface Film, that is, constitute solid-liquid film phase, and chemical reaction is just carried out in reactant and solution interface, and because in the middle of product activity Product NixMnyO2·nH2The final product LiNi that O and reactive intermediates are generated with LiOH fast reactionsxMnyO4All it is solid Body, product is crystallized from solution and generates precipitation, and reactant reduces product and also constantly reduces in liquid phase, is reacted in addition suitable When high temperature (80~200 DEG C) and enclosed environment (water yield is held essentially constant) under conditions of carry out, reactant reduce and generate The crystalline deposit of thing, the dissolving of accelerating solid reactant, and then accelerate the generation of product, therefore the generation of the precipitation of reactant Learn reaction constantly and quickly carry out, whole " solid-liquid film phase " synthetic reaction can be completed within a short period of time.
Observe the positive pole of the nickel ion doped of the technology of the present invention synthesis respectively with SEM (SEM, as follows) The pattern of material, its particle size range being counted, its pattern is approximate regular octahedron body, particle size range is about 0.25~ 5.0 μm, average grain diameter is about 1.0~3.5 μm；With EDS (Energy Dispersive Spectrometer, i.e. X-ray energy Spectrum, as follows) the technical Analysis Ni of synthetic sample:Mn mol ratios, nickel, manganese mol ratio mean ratio are 1:2.998~1: (refer to down between 3.002：" the Ni of embodiment typical case's nickel ion doped sample of present specification table 1:(EDS is determined Mn mol ratios As a result) ")；The crystal structure for synthesizing nickel lithium manganate cathode material is determined with XRD, has as a result shown that nickel ion doped material is spinelle Type crystal；Nickel ion doped material electrochemical performance is adopted with nickel ion doped material as positive active material making positive pole, to manufacture The LiPF of graphite cathode, 0.5~2.0M used by lithium ion battery6/EC:DEC:EMC=1:1:1(EC:DEC:EMC=volumes Than, wherein：EC is ethylene carbonate, and DEC is dimethyl carbonate, and EMC is methyl ethyl carbonate, as follows) solution be electrolyte, Manufactured lithium ion battery is measured, and the open-circuit voltage of battery is 4.75~5.0 volts, average discharge volt more than 4.5 volts, Measure its 0.25C charging, 0.5C discharge-rates (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) to discharge first Specific discharge capacity is 109~159mAh/g, and the highest specific discharge capacity of material is 234mAh/g.
The Ni of the embodiment of table 1 typical case's nickel ion doped sample:Mn mol ratios (EDS test results)
The explanation of table 1：1) test point that EDS tests each sample is 3~6；2) nickel in table, manganese atom percentage (the 2nd, 5 row) and nickel, manganese mol ratio (the 3rd, 6 row) are the mean value of 3~6 test results.
The present invention compared with prior art, has the advantage that and beneficial effect：
1st, LiNi prepared by the present invention0.5Mn1.5O4For Typical Representative nickel ion doped positive active material (hereinafter referred to as： Nickel lithium manganate cathode material or nickel ion doped positive active material) manufactured by lithium ion cell positive, with existing lithium from Sub- battery graphite electrode is that the Charging state lithium ion battery manufactured by negative pole has higher discharge voltage, its average discharge volt More than 4.5 volts, highest open-circuit voltage up to 5.0 volts, therefore, with the present invention prepare LiNi0.5Mn1.5O4For the nickel manganese of Typical Representative Lithium ion battery manufactured by sour lithium positive active material has and compares than existing lithium ion battery, with higher specific energy and Higher specific power.
2nd, nickel ion doped positive active material prepared by the present invention prepared by the present invention, nickel, manganese Metal element have higher Oxidation state, calculate its Average oxidation number for 3.65 by discharge capacity, highest oxidation number up to 4.0, the nickel of high oxidation state, manganese Metal The presence of ion, being conducive to the embedded quantity of lithium ion in charging process increases, and improves the specific discharge capacity of battery, therefore, make What the nickel ion doped positive active material prepared with the present invention was manufactured just has higher initial discharge specific capacity, and highest is initial Specific discharge capacity reaches 159mAh/g, and minimum initial discharge specific capacity is 138mAh/g, and average initial discharge specific capacity is 147.1mAh/g, 300 charge and discharge cycles efficiency for charge-discharges are followed more than 93% (referring to accompanying drawing 10, accompanying drawing 11), 300 discharge and recharges Ring capability retention is more than 85% (detailed in Example 7).Highest specific discharge capacity is 234mAh/g, reaches nickel ion doped theoretical (its theoretical specific capacity is 250mAh/g (being also 276mAh/g) to specific capacity, refers to document：Enhancement of the high potential specific charge in layered electrode materials for lithium-ion Batteries [J] .J.Mater.Chem.A, 2014,2,8589-8598.) 93.6%, the nickel lithium manganate cathode material of synthesis The positive pole of manufacture has preferable capacity matching relation with graphite cathode, so as to be effectively improved the utilization ratio of battery material, Reduce lithium ion battery manufacturing cost.
3rd, the crystal structure of nickel ion doped positive active material prepared by the present invention prepared by the present invention is spinel-type knot There is structure, the nickel ion doped of spinel structure three-dimensional Lithium-ion embeding/abjection passage (to refer in charge and discharge process：Document “Preparing LiNi0.5Mn1.5O4nano-plates with superior properties in lithium-ion batteries using bimetal-organic coordination-polymers as precursors[J].J. Mater.Chem.A.2014,2:9322-9330 ", document " Facile synthesis of aluminum-doped LiNi0.5Mn1.5O4hollow microspheres and their electrochemical performance for high-voltage Li-ion batteries[J].J.Alloys&Compounds.2014,609:54-59 ", document “Silicon/graphene based nano-composite anode:large-scale production and stable high capacity for lithium ion batteries[J].J.Mater.Chem.A,2014,2:9118- 9125 " and document " Size and shape control of LiFePO4nano-crystals for better lithium ion battery cathode materials[J].Nano Research.2013,6(7):469-477 "), compared with The presence of good Lithium-ion embeding passage, the conductive capability of material it is functional, greatly increase by its made mfg. electrode Conductive capability, reduces the internal resistance of manufactured lithium ion battery, be significantly increased lithium ion battery discharging efficiency and Specific discharge capacity, the highest specific discharge capacity for synthesizing positive electrode is 234mAh/g.
4th, nickel ion doped positive active material prepared by the present invention prepared by the present invention is not only tied with spinel type crystal Structure is structure, and the grain diameter of material is in 0.25~5.0 μ m, the nickel lithium manganate cathode material of the particle size range lithium from In sub- battery manufacturing process, the nano material of the single particle size that compared respectively due to particle diameter or the micron order material of single particle size With more preferable processing characteristics, larger particles form the appraisal of positive pole coating, and small-particulate materials are then filled in bulky grain skeleton Between gap, the fillibility of electrode is greatly increased, improve the compacted density of electrode, and then the lithium ion battery that improve Volume and capacity ratio and volumetric specific power and battery energy density per unit volume.
5th, the relatively simple easy, yield of the synthesis technique flow process of nickel lithium manganate cathode material of the present invention is high, product is prepared into This relatively low, content (Li of the lithium nickel manganese element of material:Ni:Mn mol ratio=1:2.999~1:And synthetic material 3.002) Grain diameter etc. is all relatively easy to control.Nickel lithium manganate cathode material prepared by the present invention has particle size distribution suitable, larger And smaller particle is evenly distributed, specific surface is larger, heat endurance is high, the tool in existing conventional lithium-ion battery electrolytes medium The features such as having good stability, initial discharge specific capacity height, have extended cycle life, in the production for not changing original lithium ion battery In the case of technique, the high-quality lithium ion two that can just utilize the production equipment manufacture production performance of original lithium ion battery excellent Primary cell.
6th, the nickel lithium manganate cathode material prepared by the present invention is properly termed as completely " environment-friendly material ", because material Any environmentally harmful solvent or additive used in manufacture process, all raw materials used also environmentally safe or Pollution is extremely low, therefore, in lithium ion cell electrode, manufacture and use all non-environmental-pollutions of lithium ion battery or extremely low environment Pollution, recovery and utilization or the harmless treatment advantage of lower cost of old and useless battery.
7th, the manufacturing process of the nickel lithium manganate cathode material prepared by the present invention is simple, and equipment synthesized without particular/special requirement The journey time is short, synthesis cycle is short, and energy consumption is low, produces almost without any pollutant and harmful, harmful by-products, is advantageously implemented collection About scale industrial production, and with good economic benefit and environmental benefit.
Description of the drawings
Fig. 1 is a kind of embodiment 1, the 2-in-1 SEM photograph (explanation into nickel lithium manganate cathode material：In SEM photograph, embodiment The multiplication factor of 1 sample is respectively 10000 and 5000 times；The multiplication factor of the sample of embodiment 2 is respectively 5000 and 7500 times.)
Fig. 2 is the SEM photograph (explanation that a kind of embodiment 3,4 synthesizes nickel lithium manganate cathode material：In SEM photograph, embodiment The multiplication factor of 3 samples is 5000 times；The multiplication factor of the sample of embodiment 4 is respectively 10000 and 5000 times.)
Fig. 3 is the SEM photograph (explanation that a kind of embodiment 5,6 synthesizes nickel lithium manganate cathode material：In SEM photograph, embodiment The multiplication factor of 5 samples is 10000 times；The multiplication factor of the sample of embodiment 6 is respectively 7500 and 5000 times.)
Fig. 4 is the SEM photograph (explanation that a kind of embodiment 7,8 synthesizes nickel lithium manganate cathode material：In SEM photograph, embodiment The multiplication factor of 7 samples is respectively 7500 and 5000 times；The multiplication factor of the sample of embodiment 8 is respectively 10000 and 5000 times.)
Fig. 5 is the SEM photograph (explanation that a kind of embodiment 9,10 synthesizes nickel lithium manganate cathode material：In SEM photograph, implement The multiplication factor of the sample of example 9 is respectively 10000 and 5000 times；The multiplication factor of the sample of embodiment 10 is 5000 times.)
Fig. 6 is the SEM photograph (explanation that a kind of embodiment 11,12 synthesizes nickel lithium manganate cathode material：In SEM photograph, implement The multiplication factor of the sample of example 11 is 5000 times；The multiplication factor of the sample of embodiment 12 is respectively 10000 and 5000 times.)
Fig. 7 is a kind of XRD (explanation of the nickel lithium manganate cathode material of the exemplary embodiments synthesis of synthesis：In XRD, Test condition be Cu targets, the θ of the angle of diffraction 2：10~80 degree；From bottom to top 12 diffraction curves are followed successively by respectively embodiment 1~to reality Apply the XRD diffraction curves of the sample of example 12.)
Fig. 8 is a kind of charging and discharging curve (explanation of the typical nickel lithium manganate cathode material of synthesis：Master map is embodiment 1 in figure The discharge curve of the first time charge and discharge cycles of the nickel lithium manganate cathode material of~embodiment 6；Upper right corner accompanying drawing is corresponding the The charge and discharge cycles curve of charge and discharge cycles.)
Fig. 9 is a kind of charging and discharging curve (explanation of the typical nickel lithium manganate cathode material of synthesis：Master map is embodiment 7 in figure The discharge curve of the first time charge and discharge cycles of the nickel lithium manganate cathode material of~embodiment 12；Upper right corner accompanying drawing is corresponding the The charge and discharge cycles curve of charge and discharge cycles.)
Figure 10 is a kind of charge/discharge capacity figure (explanation of the typical nickel lithium manganate cathode material of synthesis：Figure is the allusion quotation of embodiment 7 The variation diagram of the charge/discharge capacity of 300 charge and discharge cycles of type nickel lithium manganate cathode material.)
Figure 11 is a kind of 300 circulation discharging efficiency figure (explanations of nickel lithium manganate cathode material of synthesis：Figure is embodiment The discharging efficiency changing trend diagram of 300 charge and discharge cycles of 7 typical nickel lithium manganate cathode material, discharging efficiency=charging is held Amount/discharge capacity.)
Figure 12 is that a kind of 300 cyclic discharge capacities of nickel lithium manganate cathode material of synthesis keep efficiency chart (explanation：Figure For the discharge capacitance figure of 300 charge and discharge cycles of the typical nickel lithium manganate cathode material of embodiment 7.)
Figure 13 is a kind of solid-liquid film phase schematic diagram.
Arrow wherein to the right represents that constantly dissolving or product are continuously generated and crystalline deposit solid reactant.
Specific embodiment
With reference to embodiment, Figure of description, further detailed description is done to the present invention.
Embodiment 1:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel nitrate of 0.02mol and 0.06 manganese nitrate, the lithium acetate mixed grinding of 0.65mol, obtains To nickel, manganese, lithium mixture；
Second step by 0.084mol (equivalent to nickel salt in the first step, 1.05 times of manganese salt mole total amount) potassium peroxydisulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 1mL distilled water, plus Cover, add the sealing of stainless steel cauldron overcoat, 60 DEG C of controlling reaction temperature to be incubated 36 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with distilled water to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 650 DEG C of atmospheric environments, roasting 4 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range be 0.4~5 μm, average grain diameter is about 2.5 μm (referring to accompanying drawing 1)；Nickel is determined with EDS The Ni of lithium manganate material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.001 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electrification Performance is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The first discharge specific capacity of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (refers to figure for 141mAh/g 8)。
Embodiment 2:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step by nickel mole total amount for 0.042mol equimolar than mix nickel chloride (0.021mol), nickel nitrate (0.021mol) with manganese mole total amount for 0.12mol equimolar than the manganese chloride (0.05mol), the manganese nitrate that mix (0.05mol), the lithium hydroxide mixed grinding of 1.125mol is uniform, obtains nickel, manganese, lithium mixture；
Second step by 0.168mol (equivalent to nickel salt in the first step, 1.05 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 2mL deionized waters, plus Cover, add the sealing of stainless steel cauldron overcoat, 80 DEG C of controlling reaction temperature to be incubated 32 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with deionized to sulfate radical-free detection, suction filtration, obtains Brown or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 750 DEG C of atmospheric environments, roasting 4 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is 1.0~3.0 μm, and average grain diameter is about 2.0 μm (referring to accompanying drawing 1)；Nickel is determined with EDS The Ni of lithium manganate material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:2.998 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electrification Performance is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The electric discharge first of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (is referred to than specific capacity for 150mAh/g Fig. 8).
Embodiment 3:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel sulfate of 0.06mol and 0.18 manganese sulfate, the lithium hydroxide mixed grinding of 2.05mol, Obtain nickel, manganese, lithium mixture；
Second step by 0.264mol (equivalent to nickel salt in the first step, 1.1 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 5mL pure water, plus Cover, add the sealing of stainless steel cauldron overcoat, 100 DEG C of controlling reaction temperature to be incubated 28 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, with pure water washing to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 850 DEG C of atmospheric environments, roasting 6 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is 1.0~4.0 μm, and average grain diameter is about 2.0 μm (referring to accompanying drawing 2)；Nickel is determined with EDS The Ni of lithium manganate material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.000 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electrification Performance is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.55 volts, measures its 0.25C charging, 0.5C electric discharges The first discharge specific capacity of multiplying power (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (is referred to for 138mAh/g Fig. 8).
Embodiment 4:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel sulfate of 0.08mol and 0.24 manganese sulfate, the lithium hydroxide mixed grinding of 2.8mol, Obtain nickel, manganese, lithium mixture；
Second step by 0.368mol (equivalent to nickel salt in the first step, 1.15 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 10mL distilled water, plus Cover, add the sealing of stainless steel cauldron overcoat, 120 DEG C of controlling reaction temperature to be incubated 24 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with distilled water to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 950 DEG C of atmospheric environments, roasting 8 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is 1.0~4.0 μm, and average grain diameter is about 2.0 μm (referring to accompanying drawing 2)；Nickel is determined with EDS The Ni of lithium manganate material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:2.999 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electrification Performance is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The electric discharge first of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (is referred to than specific capacity for 145mAh/g Fig. 8).
Embodiment 5:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel sulfate of 0.12mol and 0.36 manganese sulfate, the lithium hydroxide mixed grinding of 4.55mol, Obtain nickel, manganese, lithium mixture；
Second step by 0.504mol (equivalent to nickel salt in the first step, 1.05 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 15mL pure water, plus Cover, add the sealing of stainless steel cauldron overcoat, 140 DEG C of controlling reaction temperature to be incubated 24 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, with pure water washing to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, under 850 DEG C of atmospheric environments, roasting 12 hours, from Room temperature is so cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is 1.0~5.0 μm, and average grain diameter is about 2.5 μm (referring to accompanying drawing 3)；Nickel is determined with EDS The Ni of lithium manganate material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.000 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electrification Performance is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The electric discharge first of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (is referred to than specific capacity for 149mAh/g Fig. 8).
Embodiment 6:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel sulfate of 0.17mol and 0.50 manganese sulfate, the lithium hydroxide mixed grinding of 6.05mol, Obtain nickel, manganese, lithium mixture；
Second step by 0.723mol (equivalent to nickel salt in the first step, about 1.08 times of manganese salt mole total amount) ammonium persulfate Mixture mixed grinding with described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 25mL deionized waters, Add a cover, add the sealing of stainless steel cauldron overcoat, 160 DEG C of controlling reaction temperature to be incubated 20 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with deionized to sulfate radical-free detection, suction filtration, obtains Brown or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 950 DEG C of atmospheric environments, roasting 4 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range be 0.5~3.5 μm, average grain diameter is about 1.5 μm (referring to accompanying drawing 3)；Determined with EDS The Ni of nickel ion doped material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.000 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electricity Chemical property is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The electric discharge first of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (is referred to than specific capacity for 156mAh/g Fig. 8).
Embodiment 7:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel sulfate of 0.20mol and 0.60 manganese sulfate, the lithium hydroxide mixed grinding of 8.20mol, Obtain nickel, manganese, lithium mixture；
Second step by 0.90mol (equivalent to nickel salt in the first step, 1.125 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 30mL pure water, plus Cover, add the sealing of stainless steel cauldron overcoat, 180 DEG C of controlling reaction temperature to be incubated 16 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, with pure water washing to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 950 DEG C of atmospheric environments, roasting 6 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is 0.5~4.0 μm, and average grain diameter is about 2.0 μm (referring to accompanying drawing 4)；Nickel is determined with EDS The Ni of lithium manganate material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.000 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electrification Performance is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.575 volts, measures its 0.25C charging, 0.5C and puts The first discharge specific capacity of electric multiplying power (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge is 159mAh/g (detailed See accompanying drawing 9), highest specific discharge capacity is 234mAh/g, and 300 times charge and discharge cycles efficiency for charge-discharge (refers to accompanying drawing more than 93% 10th, accompanying drawing 11), more than 85%, (minimum conservation rate is 85.77% to 300 charge and discharge cycles capability retentions, i.e. decay is less than 15%, refer to Figure 12).
Embodiment 8:
The first step is equal by the nickel sulfate of 0.222mol and 0.66 manganese sulfate, the lithium hydroxide mixed grinding of 8.82mol It is even, obtain nickel, manganese, lithium mixture；
Second step by 1.014mol (equivalent to nickel salt in the first step, 1.15 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 35mL distilled water, plus Cover, add the sealing of stainless steel cauldron overcoat, 190 DEG C of controlling reaction temperature to be incubated 12 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with distilled water to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 900 DEG C of atmospheric environments, roasting 6 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is about 0.25~2.0 μm, and average grain diameter is about 1.0 μm (referring to accompanying drawing 4)；Determined with EDS The Ni of nickel ion doped material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:2.998 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electricity Chemical property is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The first discharge specific capacity of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (refers to figure for 151mAh/g 9)。
Embodiment 9:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is uniform by the nickel sulfate of 0.24mol and 0.72 manganese sulfate, the lithium hydroxide mixed grinding of 10.4mol, Obtain nickel, manganese, lithium mixture；
Second step by 1.056mol (equivalent to nickel salt in the first step, 1.10 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 40mL pure water, plus Cover, add the sealing of stainless steel cauldron overcoat, 190 DEG C of controlling reaction temperature to be incubated 10 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, with pure water washing to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, under 950 DEG C of atmospheric environments, roasting 10 hours, from Room temperature is so cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is about 0.5~5.0 μm, and average grain diameter is about 1.0 μm (referring to accompanying drawing 5)；Determined with EDS The Ni of nickel ion doped material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.002 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electricity Chemical property is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The first discharge specific capacity of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (refers to figure for 148mAh/g 9)。
Embodiment 10:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step is equal by the lithium hydroxide mixed grinding of the manganese sulfate of the nickel sulfate of 0.25mol and 0.75mol, 11.0mol It is even, obtain nickel, manganese, lithium mixture；
Second step by 1.05mol (equivalent to nickel salt in the first step, about 1.05 times of manganese salt mole total amount) ammonium persulfate Mixture mixed grinding with described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, adds 45mL pure water, plus Cover, add the sealing of stainless steel cauldron overcoat, 190 DEG C of controlling reaction temperature to be incubated 8 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, with pure water washing to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, and under 850 DEG C of atmospheric environments, roasting 8 hours is natural Room temperature is cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is about 1.0~5.0 μm, and average grain diameter is about 1.5 μm (referring to accompanying drawing 5)；Determined with EDS The Ni of nickel ion doped material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.000 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electricity Chemical property is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The first discharge specific capacity of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (refers to figure for 143mAh/g 9)。
Embodiment 11:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step by nickel mole total amount for 0.24mol equimolar than mix nickel nitrate (0.08mol), nickel sulfate (0.08mol), nickel chloride (0.08mol) and manganese mole total amount are the equimolar of 0.72mol than the manganese nitrate that mixes (0.24mol), manganese sulfate (0.24mol), the mixture of manganese chloride (0.24mol), 11.2mol lithium acetate mixed grinding it is equal It is even, obtain nickel, manganese, lithium mixture；
Second step by 1.155mol (equivalent to nickel salt in the first step, 1.05 times of manganese salt mole total amount) ammonium persulfate with Mixture mixed grinding described in the first step, obtains reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, is added 45mL distilled water, is added Cover, add the sealing of stainless steel cauldron overcoat, 180 DEG C of controlling reaction temperature to be incubated 12 hours, the reactant for obtaining；
4th step takes out the reactant obtained by the 3rd step, is washed with distilled water to sulfate radical-free detection, suction filtration, obtains palm fibre Color or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, under 950 DEG C of atmospheric environments, roasting 12 hours, from Room temperature is so cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is about 1.0~3.0 μm, and average grain diameter is about 1.5 μm (referring to accompanying drawing 6)；Determined with EDS The Ni of nickel ion doped material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.000 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electricity Chemical property is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The first discharge specific capacity of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (is referred to attached for 140mAh/g Fig. 9).
Embodiment 12:
A kind of preparation method of nickel lithium manganate cathode material, its step is：
The first step by the nickel chloride of 0.334mol and manganese mole total amount for 1.0mol equimolar than the manganese acetate that mixes (0.25mol), manganese nitrate (0.25mol), manganese chloride (0.25mol), the mixture of manganese sulfate (0.25mol), the oxygen of 6.25mol Change lithium (Li2O wherein Li+Measure as 12.5mol) mixed grinding is uniform, obtains nickel, manganese, lithium mixture；
Second step by 1.601mol (equivalent to nickel salt in the first step, 1.2 times of manganese salt mole total amount) sodium peroxydisulfate (phase When 1.2 times of the nickel manganese mole total amount in the first step) with the mixture mixed grinding described in the first step, obtain reactant mixture；
Reactant mixture described in second step is proceeded to ptfe autoclave by the 3rd step, add 50mL deionized waters, Add a cover, add the sealing of stainless steel cauldron overcoat, 200 DEG C of controlling reaction temperature to be incubated 4 hours, the reactant for obtaining；
4th step take out the 3rd step obtained by reaction deionized water thing, be washed with deionized to sulfate radical-free detection, Suction filtration, obtains brown or black solid；
Above-mentioned brown or black solid are proceeded to again crucible by the 5th step, under 950 DEG C of atmospheric environments, roasting 12 hours, from Room temperature is so cooled to, that is, obtains nickel lithium manganate cathode material.
With SEM the pattern of nickel ion doped material being observed respectively, its particle size range has been counted, its pattern is approximate Regular octahedron body, particle size range is about 1.0~5.0 μm, and average grain diameter is about 1.5 μm (referring to accompanying drawing 6)；Determined with EDS The Ni of nickel ion doped material:Mn mol ratios, the Ni of test:Mn mol ratio mean values are：1:3.001 (refer to：Table 1)；It is fixed with XRD The crystal structure of product, as a result shows that nickel ion doped material is spinel type crystal (referring to accompanying drawing 7)；Nickel ion doped material electricity Chemical property is adopted with nickel ion doped material and makes positive pole as positive active material, born with manufacturing the graphite used by lithium ion battery Pole, the LiPF of 0.5~2.0M6/EC:DEC:EMC=1:1:1 solution is electrolyte, and manufactured lithium ion battery is surveyed Fixed, the open-circuit voltage of battery is 4.75~5.0 volts, and average discharge volt is 4.5 volts, measures its 0.25C charging, 0.5C electric discharges times The first discharge specific capacity of rate (4.0 volts of charge cutoff voltage 5.0V, final discharging voltage) electric discharge (refers to figure for 145mAh/g 9)。
Unaccomplished matter of the present invention is known technology.

Claims (6)

1. a kind of preparation method of nickel lithium manganate cathode material, its step is：
A, by the manganous salt of 0.02~0.25mol mole of divalent nickel salt and 0.06~1.0mol, Li+Molal quantity be 0.65 The lithium compound mixed grinding of~12.5mol is uniform, obtains nickel, manganese, lithium mixture；
B, mix persulfate that mole is 1.05~1.20 times of divalent nickel salt and manganous salt integral molar quantity is described with A steps Compound mixed grinding, obtains reactant mixture；
C, the described reactant mixture of B steps is proceeded to into ptfe autoclave, add 1~50mL water, add a cover, plus stainless steel it is anti- Kettle overcoat is answered to seal, 60~200 DEG C of controlling reaction temperature is incubated 4~36 hours, the reactant for obtaining；
Reactant obtained by D, taking-up C steps, is washed with water to sulfate radical-free detection, and suction filtration obtains brown or black solid；
E, brown or black solid that D steps are obtained proceed to again crucible, and under 650~950 DEG C of atmospheric environments, roasting 4~12 is little When, room temperature is naturally cooled to, obtain nickel lithium manganate cathode material.
2. the preparation method of a kind of nickel lithium manganate cathode material according to claim 1, it is characterised in that：Described two Valency nickel salt includes：One kind or two kinds to four kinds of any mixture in nickel acetate, nickel nitrate, nickel chloride or nickel sulfate.
3. the preparation method of a kind of nickel lithium manganate cathode material according to claim 1, it is characterised in that：Described two Valency manganese salt includes：One kind or two kinds to four kinds of any mixture in manganese acetate, manganese nitrate, manganese chloride, manganese sulfate.
4. the preparation method of a kind of nickel lithium manganate cathode material according to claim 1, it is characterised in that：Described lithium Compound includes：One kind or two kinds of mixing in lithia, lithium hydroxide.
5. the preparation method of a kind of nickel lithium manganate cathode material according to claim 1, it is characterised in that：Described mistake Sulfate is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate one kind therein.
6. the preparation method of a kind of nickel lithium manganate cathode material according to claim 1, it is characterised in that：Described water For the one kind in distilled water, pure water, deionized water.
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