CN106910887A - A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode - Google Patents

A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode Download PDF

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CN106910887A
CN106910887A CN201510970962.4A CN201510970962A CN106910887A CN 106910887 A CN106910887 A CN 106910887A CN 201510970962 A CN201510970962 A CN 201510970962A CN 106910887 A CN106910887 A CN 106910887A
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lithium
anode
manganese
solution
rich manganese
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CN106910887B (en
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高敏
庄卫东
王振尧
尹艳萍
卢世刚
张超
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Beijing General Research Institute for Non Ferrous Metals
China Automotive Battery Research Institute Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
China Automotive Battery Research Institute Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention discloses a kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode.The chemical formula of the lithium-rich manganese-based anode material is Li1+xMnyMzAwOr, wherein M is at least one in Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn, and A is at least one in S, P, B and F, and 0 < x≤1,0 < y≤1,0≤z < 1,0≤w≤0.2,1.8≤r≤3;The lithium-rich manganese-based anode material is obtained using the method for oxalate coprecipitation-spray drying-high-temperature roasting.Instant invention overcomes material agglomeration prepared by oxalate coprecipitation method, prepared material particle size is controllable, reaches engineering index request, and can realize that transition metal ions is well mixed in atomic level;3-25 μm prepared of lithium-rich manganese-based anode material particle diameter, while have both good high rate performance and cycle performance, and preparation process is simple, low cost, application prospect are wide.

Description

A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode
Technical field
A kind of lithium the present invention relates to lithium-rich manganese-based anode material, its preparation method and comprising the positive electrode from Sub- battery, belongs to anode material for lithium-ion batteries and its preparation field.
Background technology
Lithium ion battery is widely used in notebook computer, moves as a kind of novel high-energy green battery On the portable type electronic products such as mobile phone, and expanded to fields such as big-and-middle-sized energy storage device and new energy electric motor vehicles, This proposes requirement higher to lithium ion battery energy density, cycle life, cost and security etc.. Positive electrode is the important component of lithium ion battery, accounts for 30%-40% of whole battery totle drilling cost or so. Therefore, the performance and its cost of reduction for improving positive electrode are extremely crucial for the development of lithium ion battery.Its In, lithium-rich manganese-based anode material Li1+x(MnM)1-xO2(M=Ni, Co, Cr, Fe......, 0 < x≤1/3) 250mAhg (is more than with its specific discharge capacity high-1) be considered as current high energy density cells candidate One of positive electrode.
Have been developed the method that much prepares lithium-rich manganese-based anode material at present, such as hydro-thermal method, solid phase method, Coprecipitation etc..Hydro-thermal method is easily-synthesized the active material of nano particle, shortens lithium ion diffusion path to improve The chemical property (Adv.Mater.22 (2010) 4364-4367) of material, but preparation technology is cumbersome, causes The volume energy density of Engineering operation inconvenience and material declines.Solid phase method holds when preparing lithium-rich manganese-based anode material Easily there is transition metal and mix uneven, required temperature is higher, and product morphology is not easily controlled, and is unfavorable for Product chemical property (Electrochimica Acta, 91,2013,214-218) is controlled by synthesizing.Its In, coprecipitation prepares lithium-rich manganese-based anode material and generally uses.The B of patent CN 102544475 and The B of CN 102627332 propose and prepare rich lithium material using the method for oxalate coprecipitation, it is to avoid hydroxide Coprecipitation process operates poor repeatability, manganous hydroxide (+divalent) rapid oxidation institute band in atmosphere in objects system The problem of the product property fluctuation for coming, but the material prepared by oxalate coprecipitation is easy in drying process There is hardened phenomenon of reuniting so that material morphology and particle diameter are uncontrollable, be unfavorable for that engineering makes processing (Journal of The Electrochemical Society, 160 (5) (2013) A3108-A3112).Additionally, During material prepared by oxalate coprecipitation method, it is required for obtained precursor washing process, purpose It is to remove out Na+、SO4 2-Deng foreign ion.But, occur with washing transition metal ions different degrees of It is lost in, causes waste of raw materials, causes the ratio of transition metal ions to deviate from chemical meter most serious of all Amount, so as to cannot be controlled to the phase composition of the component of transition metal ions and final synthetic product.
The content of the invention
It is an object of the invention to provide a kind of lithium-rich manganese-based anode material, by modified technique process, solve Material morphology, granularity and the uncontrollable problem of precise chemical structure component.
Another object of the present invention is to provide a kind of preparation method of the lithium-rich manganese-based anode material, the system Preparation Method flow is simple, can realize that lithium-rich manganese-based anode material pattern, granularity and precise chemical structure component are controllable.
It is yet a further object of the present invention to provide the lithium ion battery comprising the lithium-rich manganese-based anode material.
To achieve the above object, the present invention uses following technical scheme:
A kind of lithium-rich manganese-based anode material, the chemical formula of the lithium-rich manganese-based anode material is Li1+xMnyMzAwOr, Wherein M is at least in Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn Kind, A is at least one in S, P, B and F, and 0 < x≤1,0 < y≤1,0≤z < 1,0≤w ≤ 0.2,1.8≤r≤3;The lithium-rich manganese-based anode material uses oxalate coprecipitation-spray drying-high-temperature roasting Method be obtained.
The microstructure of the lithium-rich anode material is Li2MnO3And LiMO2Layered composite structure, wherein, M is at least one in Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn.
A kind of preparation method of the lithium-rich manganese-based anode material, at least comprises the following steps:
(1) corresponding raw material is weighed by the mol ratio of chemical formula, by the solution containing manganese source and M sources and containing oxalic acid The solution of radical ion carries out mixing co-precipitation, and controls mixing condition, obtains precursor pulp;
(2) step (1) gained precursor pulp is spray-dried, is obtained presoma powder;
(3) step (2) gained presoma powder, lithium source and A sources are mixed, and mixture high temperature is roasted Burning obtains lithium-rich manganese-based anode material.
Wherein, the manganese source is manganese acetate and/or manganese nitrate;The M sources are the acetate or nitrate of M In at least one;The solution containing oxalate denominationby for oxalic acid solution, oxalic acid and ammoniacal liquor mixed solution, At least one in the mixed solution of ammonium oxalate solution or ammonium oxalate and ammoniacal liquor;The lithium source is lithium carbonate, hydrogen At least one in lithia, lithium nitrate, lithium acetate and lithium fluoride;The A sources are the ammonium salt or lithium salts of A In at least one.
In the step (1), addition ammonia spirit is co-precipitated;The mixing condition for being controlled is:Stir Speed is mixed for 50-1200rpm, reaction temperature is room temperature to 85 DEG C, reaction time >=4h.
The concentration of the solution containing oxalate denominationby is 0.1-1.5mol/L;Manganese in the solution in manganese source and M sources It is 0.1-1.5mol/L with the total concentration of M ions.
The solid content of the precursor pulp is 10g/L-300g/L, and EAT during spray drying is 150 DEG C -280℃;The ammonium acetate class or nitric acid ammonium material that gas condensation discharged in spray-drying process is obtained can be returned Receive and utilize.
Further include to carry out at Low Temperature Thermal gained presoma powder between step (2) and step (3) The step of reason.The condition of the Low Temperature Heat Treatment is:1-20h is incubated at 100-300 DEG C, then is warming up to 300-500 DEG C insulation 1-20h.
Mixture high-temperature roasting condition is in the step (3):Sintering temperature is 700-1000 DEG C, during insulation Between be 5-30h.
A kind of lithium ion battery, comprising described lithium-rich manganese-based anode material, negative pole and between both positive and negative polarity it Between isolated substance.Wherein, the isolated substance contains barrier film and liquid electrolyte or gel polymer electrolyte Matter or total solids electrolyte.
The beneficial effects of the invention are as follows:
(1) present invention prepares presoma using oxalate coprecipitation, and reactant reacts in the liquid phase, realizes Mixing on atom or molecular level;Meanwhile, oxalate coprecipitation is overcome using the method for spray drying Material agglomeration prepared by method, there is hardened problem in material after especially drying, and realizes second particle Spheroidization, size tunable is 3-25 μm, with preferable mobility, reaches engineering use requirement.
(2) coprecipitation method cannot transition metal ions amount in precise control precursor, with the material after lithium roasting Easily there are the impurities phases such as nickel oxide or Mn oxide in material, cannot more realize lithium-rich manganese base material crystal structure Control synthesis, cause material electrochemical performance to reduce.The preparation side of lithium-rich manganese base material proposed by the present invention Method, eliminates the component damages that co-precipitation is caused due to washing, and saved a large amount of using drying process with atomizing Slurry.NO is removed in reaction system3 -、CH3COO-、NH4 +Outside be not introduced into other impurities ion, While so that precipitation reaction is effectively carried out, using CH3COONH4Or NH4NO3In heat treatment process meeting Decompose, will not leave behind impurity after treatment in system;Therefore, precipitated product is not required to washing, nickel in preparation technology Manganese cobalt is not lost in, and realizes the chemical composition and crystal structure precise control of material.
(3) this invention simplifies the technological process that oxalate coprecipitation method prepares lithium-rich manganese base material slurry, carry High efficiency and operability.The A of patent document CN 102730761 mention pH during oxalate coprecipitation Must adjust between 6.5-8.0.The present invention in the experimental basis for continuing to optimize oxalate coprecipitation reaction mechanism, Process simplification, without regulation pH, by controlling ammoniacal liquor rate of addition can the required slurry of synthesis, It is effective to improve reaction efficiency.
(4) present invention combines preparation technology the optimization of material granule microscopic appearance and crystal structure are changed simultaneously It is kind, its cyclical stability is improved, reach electrochemistry of the high-energy type lithium ion battery to positive electrode active materials Can be with the requirement of engineering technology index.
Brief description of the drawings
Fig. 1 is the XRD diffracting spectrums of lithium-rich manganese-based anode material prepared by embodiment 1 and comparative example.
Fig. 2 is the scanning electron microscope (SEM) photograph of lithium-rich manganese-based anode material prepared by embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of lithium-rich manganese-based anode material prepared by comparative example.
Fig. 4 is the first charge-discharge curve of lithium-rich manganese-based anode material prepared by embodiment 1 and comparative example.
Fig. 5 is the cycle performance figure of lithium-rich manganese-based anode material prepared by embodiment 1 and comparative example.
Specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but the implementation method invented is not It is only limitted to this.
Embodiment 1
(1) by molecular formula Li1.2Mn0.54Ni0.13Co0.11Al0.02O2In transition metal mol ratio by acetic acid Aluminium, nickel acetate, cobalt acetate and manganese acetate are configured to total transition metal ions concentration for 1.0molL-1Mixing Solution, wherein, Al: Co: Ni: Mn=0.025: 0.140: 0.165: 0.67;It is configured to 1.0molL-1Oxalic acid it is molten Liquid, configures 1molL-1NH4OH solution, three kinds of solution instill what is be stirred continuously with certain flow simultaneously In reactor;Control reaction condition:Temperature is 60 DEG C, and mixing speed is 1200rpm, during coprecipitation reaction Between 10h;
(2) gained slurry solids concentration is adjusted to 150g/L, is spray-dried at 160 DEG C, before obtaining Drive body Ni0.165Co0.140Al0.025Mn0.67C2O4·2H2O;
(3) above-mentioned oxalate precursor powder is incubated 4 hours at 320 DEG C, then is warming up to 500 DEG C of insulations 3 hours, obtain oxide precursor;
(4) example Li: (Ni+Mn+Co+Al)=1.5: 1 in molar ratio, by LiOHH2Before O and above oxide Drive body carries out batch mixing and obtains mixture, is placed in stove and is incubated 15h at 950 DEG C, and furnace cooling is obtained final product to room temperature Lithium-rich manganese-based anode material Li1.2Mn0.54Ni0.13Co0.11Al0.02O2
(5) by target product Li1.2Mn0.54Ni0.13Co0.11Al0.02O2Positive electrode and conductive agent acetylene black, Binding agent PVDF (Kynoar) is 8: 1: 1 well mixed according to mass ratio, then with NMP (N- Methyl-pyrrolidon) slurry of certain viscosity is mixed into, slurry is coated uniformly on Al paper tinsels, at 100 DEG C 2h is dried, the electrode slice of a diameter of 14mm is washed into, 80 DEG C of vacuum is carried out after rolling and is dried 10h.By the electricity Pole piece is moved in glove box, and as positive plate, then with metal lithium sheet as negative pole, the films of Celgard 2400 are barrier film, 1mol·L-1LiPF6/ EC+DEC+DMC (volume ratio 1: 1: 1) is electrolyte, in glove box (Germany M.Braun companies, O2And H2O mass fractions are respectively less than 0.1ppm) 2032 button cells of middle assembling, institute The battery of assembling carries out charge-discharge test (Wuhan, China Jin Nuo Co., Ltds) on CT2001 indigo plant electric testers, 25 DEG C ± 3 DEG C of temperature.
The X diffraction ray analysis figures of the target product and presoma are as shown in figure 1, from Fig. 1 to find out, be somebody's turn to do The main diffraction maximum of product can all be demarcated as α-NaFeO2(space group is structure), show the rich lithium material Predominantly LiMO2Layer structure;Wherein, the diffraction maximum at 2 θ=20~25 ° is by transition metal ions layer Li+With transition metal ions Mn4+Superlattices arrangement cause, the superlattice structure shows in the rich lithium material There is Li2MnO3Structure microcell.The scanning electron microscope sem figure of the target product, as shown in Fig. 2 can see Go out, the second particle size of resulting product is 3-12 μm or so of spheric granules.
Electro-chemical test shows that initial charge, specific discharge capacity divide in 0.1C, 2.0-4.8V voltage range Not Wei 322.2 and 275.8mAh/g, first charge-discharge efficiency is 85.6%, as shown in Figure 4;2.0C, First discharge specific capacity is 214.5mAh/g under the conditions of 2.5-4.7V, and specific discharge capacity is after 100 circulations 201.6mAh/g, capability retention is 95%, as shown in Figure 5.
Embodiment 2
(1) by molecular formula Li1.16Mn0.56Ni0.16Co0.08F0.02O1.98In transition metal mol ratio by acetic acid Nickel, cobalt acetate and manganese acetate are configured to total transition metal ions concentration for 1.0molL-1Mixed solution, its In, Ni: Co: Mn=0.2: 0.1: 0.7;It is configured to 1.0molL-1NH4HC2H4Solution, configures 0.5molL-1 NH4OH solution;Above-mentioned three kinds of solution to instill with certain flow the reactor being stirred continuously simultaneously in, Control reaction condition:Reaction temperature is 80 DEG C, and mixing speed is 800rpm, reaction time 10h;
(2) gained slurry solids concentration is adjusted to 250g/L, is spray-dried at 170 DEG C, before obtaining Drive body Ni0.2Co0.1Mn0.7C2H4·2H2O;
(3) above-mentioned presoma powder is incubated 4 hours at 200 DEG C, then is warming up to 400 DEG C and be incubated 3 hours, Obtain oxide precursor;
(4) example Li: (Ni+Mn+Co)=1.45: 1 in molar ratio, by LiNO3: LiF=49: 1 with above-mentioned oxide Presoma batch mixing obtains mixture, and the mixture is incubated into 30h in 400 DEG C, and then furnace cooling is to room temperature, It is placed in again in stove and is incubated 25h at 800 DEG C, furnace cooling obtains final product lithium-rich manganese-based anode material to room temperature Li1.16Mn0.56Ni0.16Co0.08F0.02O1.98, second particle particle diameter is 3-8 μm;
(5) with embodiment 1 the step of (5).
Electro-chemical test shows that first discharge specific capacity is 258.2 in 0.1C, 2.0-4.8V voltage range MAh/g, first discharge specific capacity is 220.1mAh/g, 100 circulations under the conditions of 2.0C, 2.5-4.7V Specific discharge capacity is 208.7mAh/g afterwards, and capability retention is 94.8%.
Embodiment 3
(1) by molecular formula Li1.167Mn0.533Ni0.2Co0.1O2In transition metal mol ratio by nickel acetate, Cobalt acetate is configured to total transition metal ions concentration for 1.0molL with manganese acetate-1Mixed solution, wherein, Ni: Co: Mn=0.24: 0.12: 0.64, it is configured to 1.0molL-1(NH4)2C2H4Solution, configures 4molL-1 NH4OH solution;Above-mentioned three kinds of solution to instill with certain flow the reactor being stirred continuously simultaneously in, Control reaction condition:Reaction temperature is 30 DEG C, and mixing speed is 400rpm, reaction time 4h;
(2) gained slurry solids concentration is adjusted to 300g/L, is spray-dried at 180 DEG C, before obtaining Drive body Ni0.24Co0.12Mn0.64C2H4.2H2O;
(3) above-mentioned presoma powder is incubated 4 hours at 150 DEG C, then is warming up to 450 DEG C and be incubated 3 hours, Obtain oxide precursor;
(4) example Li: (Ni+Mn+Co)=1.4: 1 in molar ratio, by lithium acetate and above-mentioned oxide precursor batch mixing Mixture is obtained, the mixture is incubated 30h in 300 DEG C, then furnace cooling is to room temperature, then is placed in stove In be incubated 5h at 700 DEG C, furnace cooling obtains final product lithium-rich manganese-based anode material to room temperature Li1.167Mn0.533Ni0.2Co0.1O2, particle diameter distribution is 3-5 μm;
(5) with embodiment 1 the step of (5).
Electro-chemical test shows that first discharge specific capacity is 268.2 in 0.1C, 2.0-4.8V voltage range MAh/g, first discharge specific capacity is 225.2mAh/g, 100 circulations under the conditions of 2.0C, 2.5-4.7V Specific discharge capacity is 191.5mAh/g afterwards, and capability retention is 85%.
Embodiment 4
(1) by molecular formula Li1.12Mn0.58Ni0.24Mg0.01P0.01O1.99In transition metal mol ratio by vinegar Sour nickel, manganese acetate, magnesium acetate are configured to total transition metal ions concentration for 1.0molL-1Mixed solution, Wherein, Ni: Mn: Mg=0.288: 0.7: 0.012, it is configured to 1.0molL-1Oxalic acid solution, configure 0.1molL-1 NH4OH solution;Above-mentioned three kinds of solution to instill with certain flow the reactor being stirred continuously simultaneously in, Control reaction condition:Reaction temperature is 30 DEG C, and mixing speed is 100rpm;
(2) gained slurry solids concentration is adjusted to 150g/L, is spray-dried at 180 DEG C, before obtaining Drive body Mn0.700Ni0.288Mg0.012C2H4·2H2O;
(3) above-mentioned presoma powder is incubated 1 hour at 200 DEG C, then is warming up to 450 DEG C and be incubated 6 hours, Obtain oxide precursor;
(4) in molar ratio example Li: (Ni+Mn+Mg): P=1.35: 1: 0.077, by lithium hydroxide, above-mentioned oxidation Thing presoma, ammonium hydrogen phosphate batch mixing obtain mixture, and the mixture is incubated into 5h, Ran Housui in 600 DEG C Stove is cooled to room temperature, then is placed in stove in 700 DEG C of insulation 8h, and furnace cooling is obtained final product lithium-rich manganese-based to room temperature Positive electrode Li1.12Mn0.58Ni0.24Mg0.01P0.01O1.99, particle diameter distribution is 10-15 μm;
(5) with embodiment 1 the step of (5).
Electro-chemical test shows that first discharge specific capacity is 238.2 in 0.1C, 2.0-4.8V voltage range MAh/g, first discharge specific capacity is 187.3mAh/g, 100 circulations under the conditions of 2.0C, 2.5-4.7V Specific discharge capacity is 168.3mAh/g afterwards, and capability retention is 90%.
Embodiment 5
(1) by molecular formula Li1.13Ni0.30Mn0.57O2In transition metal mol ratio by nickel nitrate, manganese nitrate Total transition metal ions concentration is configured to for 0.5molL-1Mixed solution, wherein, Ni: Mn=0.35: 0.65; It is configured to 0.5molL-1Oxalic acid solution, configure 0.1molL-1NH4OH solution;It is molten by above-mentioned three kinds Liquid is instilled in the reactor being stirred continuously simultaneously with certain flow, controls reaction condition:Reaction temperature is 30 DEG C, mixing speed is 600rpm;
(2) gained slurry solids concentration is adjusted to 20g/L, is spray-dried at 220 DEG C, before obtaining Drive body Ni0.35Mn0.65C2H4·2H2O;
(3) example Li: (Ni+Mn)=1.30: 1 in molar ratio, above-mentioned presoma, lithium carbonate batch mixing are mixed Compound is placed in stove and is incubated 12h at 800 DEG C, and furnace cooling obtains final product lithium-rich manganese-based anode material to room temperature Li1.13Ni0.30Mn0.57O2, particle diameter distribution is 3-8 μm;
(4) with embodiment 1 the step of (5).
Electro-chemical test shows that first discharge specific capacity is 250 in 0.1C, 2.0-4.8V voltage range MAh/g, first discharge specific capacity is 190mAh/g under the conditions of 2.0C, 2.5-4.7V, after 100 circulations Specific discharge capacity is 178.6mAh/g, and capability retention is 94.6%.
Embodiment 6
(1) by molecular formula Li1.2Mn0.6Ni0.20O2In transition metal mol ratio by nickel acetate and manganese acetate Total transition metal ions concentration is configured to for 0.5molL-1Mixed solution, wherein, Ni: Mn=0.25: 0.75, It is configured to 0.5molL-1Oxalic acid ammonia solution;The certain flow of above-mentioned solution is instilled what is be stirred continuously simultaneously In reactor, reaction condition is controlled:Reaction temperature is 60 DEG C, and mixing speed is 1000rpm;
(2) gained slurry solids concentration is adjusted to 100g/L, is spray-dried at 250 DEG C, before obtaining Drive body Ni0.25Mn0.75C2H4·2H2O;
(3) example Li: (Ni+Mn)=1.5: 1 in molar ratio, lithium hydroxide is mixed with above-mentioned presoma batch mixing Compound, 5h is incubated by the mixture in 500 DEG C, and then furnace cooling is to room temperature, then is placed in stove 900 DEG C insulation 12h, furnace cooling obtains final product lithium-rich manganese-based anode material Li to room temperature1.2Mn0.60Ni0.20O2
(4) with embodiment 1 the step of (5).
Electro-chemical test shows that first discharge specific capacity is 260.2 in 0.1C, 2.0-4.8V voltage range MAh/g, first discharge specific capacity is 200.6mAh/g, 100 circulations under the conditions of 2.0C, 2.5-4.7V Specific discharge capacity is 194.0mAh/g afterwards, and capability retention is 92%.
Comparative example
Positive electrode Li is prepared using traditional oxalic acid coprecipitation1.2Ni0.2Mn0.6O2
(1) by molecular formula Li1.2Mn0.6Ni0.20O2In transition metal mol ratio by nickel acetate and manganese acetate Total transition metal ions concentration is configured to for 1.5molL-1Mixed solution, wherein, Ni: Mn=0.25: 0.75, It is configured to 1.5molL-1Oxalic acid solution, configure 1.5molL-1NH4OH solution;It is molten by above-mentioned three kinds Liquid is instilled in the reactor being stirred continuously simultaneously with certain flow, controls reaction condition:Solution ph is 4, Reaction temperature is 60 DEG C, and mixing speed is 1000rpm;
(2) by gained slurry by suction filtration, washing is vacuum dried 12h, before obtaining oxalates at 120 DEG C Drive body Ni0.25Mn0.75C2H4·2H2O;
(3) example Li: (Ni+Mn)=1.5: 1 in molar ratio, mixture is obtained by lithium hydroxide and precursor batch mixing, The mixture is incubated 5h in 500 DEG C, then furnace cooling is to room temperature, then is placed in stove in 900 DEG C of insulations 8h, furnace cooling obtains final product traditional lithium-rich manganese-based anode material Li to room temperature1.2Mn0.60Ni0.20O2, crystal knot Structure is as shown in figure 1, pattern is as shown in Figure 3;
(4) with embodiment 1 the step of (5).
Electro-chemical test shows that first discharge specific capacity is 240.1 in 0.1C, 2.0-4.8V voltage range MAh/g, first discharge specific capacity is 187.3mAh/g, 50 circulations under the conditions of 2.0C, 2.5-4.7V Specific discharge capacity is 147.0mAh/g afterwards, and capability retention is 78%.

Claims (14)

1. a kind of lithium-rich manganese-based anode material, it is characterised in that the chemical formula of the lithium-rich manganese-based anode material is Li1+xMnyMzAwOr, wherein M is Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru With at least one in Sn, A is at least one in S, P, B and F, and 0 < x≤1,0 < y≤1, 0≤z < 1,0≤w≤0.2,1.8≤r≤3;The lithium-rich manganese-based anode material uses oxalate coprecipitation-spraying The method of drying-high-temperature roasting is obtained.
2. lithium-rich manganese-based anode material as claimed in claim 1, it is characterised in that it is described it is lithium-rich manganese-based just The second particle of pole material is spherical or spherical.
3. lithium-rich manganese-based anode material as claimed in claim 1, it is characterised in that the lithium-rich anode material The microstructure of material is Li2MnO3And LiMO2Layered composite structure, wherein, M be Ni, Co, Al, At least one in Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn.
4. the preparation method of the lithium-rich manganese-based anode material any one of a kind of claim 1-3, it is special Levy and be, at least comprise the following steps:
(1) corresponding raw material is weighed by the mol ratio of chemical formula, by the solution containing manganese source and M sources and containing oxalic acid The solution of radical ion carries out mixing co-precipitation, and controls mixing condition, obtains precursor pulp;
(2) step (1) gained precursor pulp is spray-dried, is obtained presoma powder;
(3) step (2) gained presoma powder, lithium source and A sources are mixed, and mixture high temperature is roasted Burning obtains lithium-rich manganese-based anode material.
5. preparation method as claimed in claim 4, it is characterised in that the manganese source is manganese acetate or nitric acid At least one in manganese;The M sources are at least one in the acetate or nitrate of M;It is described containing oxalic acid The solution of radical ion is mixed solution, ammonium oxalate solution or ammonium oxalate and the ammonia of oxalic acid solution, oxalic acid and ammoniacal liquor At least one in the mixed solution of water;The lithium source is lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate With at least one in lithium fluoride;The A sources are at least one in the ammonium salt or lithium salts of A.
6. preparation method as claimed in claim 4, it is characterised in that addition ammonia in the step (1) The aqueous solution is co-precipitated.
7. preparation method as claimed in claim 4, it is characterised in that control in the step (1) Mixing condition is:Mixing speed is 50-1200rpm, and reaction temperature is room temperature to 85 DEG C, reaction time >=4h.
8. preparation method as claimed in claim 4, it is characterised in that the solution containing oxalate denominationby Concentration be 0.1-1.5mol/L;The total concentration of manganese and M ions is 0.1-1.5 in the solution in manganese source and M sources mol/L。
9. preparation method as claimed in claim 4, it is characterised in that the solid content of the precursor pulp It is 10g/L-300g/L, EAT during spray drying is 150 DEG C -280 DEG C.
10. preparation method as claimed in claim 4, it is characterised in that in step (2) and step (3) Between further include the step of Low Temperature Heat Treatment is carried out to gained presoma powder.
11. preparation methods as claimed in claim 10, it is characterised in that the condition of the Low Temperature Heat Treatment For:1-20h is incubated at 100-300 DEG C, then is warming up to 300-500 DEG C of insulation 1-20h.
12. preparation methods as claimed in claim 4, it is characterised in that mixture in the step (3) High-temperature roasting condition is:Sintering temperature is 700-1000 DEG C, and soaking time is 5-30h.
13. a kind of lithium ion batteries, it is characterised in that comprising the rich lithium any one of claim 1-3 Manganese-based anode material, negative pole and the isolated substance between both positive and negative polarity.
14. batteries according to claim 13, it is characterised in that the isolated substance contain barrier film and Liquid electrolyte or gel polymer electrolyte or total solids electrolyte.
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