CN106602024A - In-situ surface-modified lithium-rich material and preparation method thereof - Google Patents

In-situ surface-modified lithium-rich material and preparation method thereof Download PDF

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CN106602024A
CN106602024A CN201611237904.1A CN201611237904A CN106602024A CN 106602024 A CN106602024 A CN 106602024A CN 201611237904 A CN201611237904 A CN 201611237904A CN 106602024 A CN106602024 A CN 106602024A
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lithium
phosphate
modification type
rich
situ modification
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CN106602024B (en
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王振尧
高敏
卢世刚
庄卫东
任志敏
尹艳萍
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China Automotive Battery Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—BASIC 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—BASIC 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—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic slats or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an in-situ surface-modified lithium-rich material. Raw materials include a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate; and the lithium-rich material precursor is a mixture of at least one of an MnMA oxide, hydroxide, carbonate and oxalate and a lithium source, wherein M is a metal element and A is at least one of S, P, B and F. The invention further discloses a preparation method. A metal phosphate compound coats lithium-rich material precursor particles and then the in-situ modified lithium-rich material is formed through high-temperature sintering. The in-situ surface-modified lithium-rich material has the advantages that the surface stability and the conductivity of the lithium-rich material are greatly improved by an in-situ modified structure; the charge-discharge specific capacity, the efficiency, the rate and the cycle performance of the material are obviously improved; and the in-situ surface-modified lithium-rich material is simple in preparation process, low in cost, good in result reproducibility and suitable for large-scale popularization.

Description

A kind of surface in situ modification type richness lithium material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, specially a kind of surface in situ modification type richness lithium material and its preparation Method.
Background technology
Lithium ion battery because energy density is high, have extended cycle life, environmental protection, low cost the features such as, in 20 years In obtained swift and violent development, its application be related to the numerous areas such as communication, traffic, military affairs, medical treatment, amusement.Recently as The fast development of electric automobile etc., high specific energy, high power lithium ion cell become the inevitable direction of following lithium ion battery development. Current business-like positive electrode, such as LiCoO2、LiFePO4、LiMn2O4, ternary material etc., specific capacity it is relatively low (<200mAh/ g).And positive electrode is the principal element for limiting battery specific energy, therefore in order to develop high specific energy batteries, it is felt to be desirable to find Positive electrode with more height ratio capacity.
In recent years, the features such as having specific capacity height, good safety, low cost due to rich lithium material, rich lithium material is caused The extensive concern of people.Its specific capacity is generally more than 250mAh/g, and 300mAh/g (Nano have been even up in the report having Lett.,2008,8(3):957-961).Although rich lithium material capacity is high, its cycle performance is poor, and exists serious Voltage droop problem, so as to constrain its business-like application.Therefore need to be modified rich lithium material, to improve its circulation During specific capacity and voltage retention.
The main method for improving rich lithium material chemical property at present be coat and adulterate (Adv.Mater.2012,24, 1192–1196；Adv.Funct.Mater.2014,1-7).Modal method for coating is using Al (OH)3、Al2O3、TiO2Deng Inert material carries out Surface coating (Electrochimica Acta 50 (2005) 4784-4791, Journal to rich lithium material The 1334-1339 of of Power Sources 159 (2006)), these claddings typically serve to protect rich lithium material surface texture, resistance Only material and electrolyte contacts and there is the effect of negative response, the first charge-discharge effect of rich lithium material is improve to a certain extent Rate and cycle performance.The patent of the A of Publication No. CN 103035906 is coated on Li [Li using wet method(1-2x)/3MxMn(2-x)/3] O2Surface coating 3-10wt% LiMnPO4, be conducive to the raising of material high rate performance, and LiMnPO4In PO4 3-Can have Effect suppresses electrode material dissolving in the electrolytic solution, prevents corrosion of the Fluohydric acid. to surface of active material in electrolyte, improves material The thermodynamic stability of material.Technical scheme disclosed in the patent of Publication No. CN101859887 is to wrap using on positive electrode Phosphate is covered, protection materials, and the effect for improving capacity and high rate performance can be played.Publication No. CN 103904311A Patent disclosed in technical scheme be, in one layer of LiFePO4 of Surface coating of rich lithium material finished product, wherein used by LiFePO4 Lithium of the lithium source in rich lithium material, as a result shows the lithium for reducing " more than needed " in rich lithium material, is conducive to stablizing for material structure, But the rear cladding that this employing liquid phase method is carried out on rich lithium material finished product, needs are first immersed in the finished product of rich lithium material molten Liquid, then again through a series of processing procedures such as precipitation, filtration, washing, drying, heat treatments, method is complex.Also deposit in addition The problems such as clad is uneven, clad is not fine and close enough with the conjugation of rich lithium material.So can not fundamentally reduce or Suppress the precipitation of oxygen and the migration of transition metal, thus cannot effectively solving material cycle performance difference and voltage attenuation etc. ask Topic.
Research done by above-mentioned structural stability and chemical property to improve rich lithium material, although to a certain degree On, realizing improves the beneficial effect of capacity and high rate performance, but comprehensive market considers, while rich lithium material is improved, system Preparation Method is simple, and selected the cost of material is low, be only it is a kind of can the method promoted of the marketization, in field of lithium, assistant officer waits to solve Technical problem certainly be set up it is a kind of it is simple, effectively, be easy to large-scale promotion surface modification cladding is carried out to rich lithium material Method, the lithium battery product high so as to obtain cycle life height, specific capacity, high rate performance.
The content of the invention
To solve above-mentioned technical problem, the invention provides a kind of surface in situ modification type richness lithium material and its preparation side Method, realizes the surface stability and electrical conductivity for improving rich lithium material, makes the charging and discharging capacity of material, efficiency, multiplying power and follows The purpose that ring performance is all improved significantly.
To achieve these goals, technical scheme disclosed by the invention is：A kind of surface in situ that the present invention is developed is repaiied Decorations type richness lithium material, raw material includes clad, rich lithium material presoma, and the clad is metal phosphate, rich lithium material Presoma is the mixture of at least one and lithium source in oxide, hydroxide, carbonate, the oxalates of MnMA, and wherein M is Metallic element, A is at least one in S, P, B and F.Coated in rich lithium material presoma from metal tripolyphosphate salt, clad Uniformly, conjugation is high, and clad can occur interfacial reaction with the raw material of rich lithium material, formed conductivity it is higher containing in lithium Interbed (inter layer), so as to improve the ionic conductivity and chemical property of material.
Further, the metal phosphate is that Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni are corresponding with Mo At least one of phosphate.Selected metal phosphate, can coat to rich lithium material presoma, obtain discharge and recharge The high rich lithium material of specific capacity, efficiency, multiplying power and cycle performance.
Further, the metal M in the rich lithium material presoma be Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, At least one in Ru and Sn.
Further, the lithium source be Lithium hydrate, lithium carbonate, lithium acetate, lithium nitrate at least one, wherein Li with The mol ratio of MnMA is 1-2.5：1.
Further, in the raw material clad mole percentage ratio be 0.01%-12%, the rich lithium material forerunner The mole percentage ratio of body is 88%-99.99%.Selected cladding mole percentage ratio has taken into account the thickness of material clad With the performance of material property, the rich lithium material checking that Jing subsequent steps are obtained, charging and discharging capacity, efficiency, multiplying power can be obtained The material high with cycle performance, former material doses used at the same time is minimum, with low cost.
Further, the chemical formula of the in-situ modification type richness lithium material that the present invention is obtained is (1-a) Li1+ xMnyMzAwOr-aLibMecPO4, wherein, 0.0001≤a≤0.12,0≤b≤3,0≤c≤1.5,0 ＜ x≤1,0 ＜ y≤1,0≤ Z ＜ 1,0≤w≤0.2,1.8≤r≤3.
The invention also discloses the method for preparing above-mentioned rich lithium material, coats metal phosphorus in rich lithium material precursor particle Barbiturates compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.The original position obtained by this method for coating Equably, and clad has good conjugation and stability to the clad of cladded type richness lithium material with rich lithium material, effectively The negative response for preventing rich lithium material to produce because of contact with electrolyte；Simultaneously using " unnecessary " in rich lithium precursor lithium source with There is " original position " chemical reaction in clad material, form a kind of high conductivity layer containing lithium.So as to significantly improve rich lithium material Discharge capacity, first charge-discharge efficiency, high rate performance, and effectively improve cycle performance and voltage attenuation of material etc. and ask Topic.
Further, the method comprises the steps that soluble phosphoric acid salt is added into rich lithium material presoma by (1) In, Deca soluble metal salt solution while stirring；The mole of wherein soluble phosphate is the 1-3 of soluble metallic salt Times, soluble metallic salt is 0.0001-0.12 with rich lithium material presoma mol ratio：0.9999-0.88.
(2) mixed solution for obtaining step (1) continues to stir, and is then dried process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material.
Further, soluble metal salt solution concentration is 0.001-10mol/ in step (1) described in the step (1) L, the concentration of soluble phosphoric acid salt solution is 0.001-10mol/L, and selected mass concentration is easy to dissolving, Jing subsequent steps Rich lithium material checking is obtained, the high material of charging and discharging capacity, efficiency, multiplying power and cycle performance can be obtained, obtaining beneficial It is minimum that effect obtains former material doses used at the same time, with low cost.
Further, soluble phosphate includes phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen two in the step (1) At least one of ammonium, sodium phosphate, potassium phosphate.
Further, in the step (1) soluble metallic salt be Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, At least one in the soluble-salt of Ni and Mo.
Further, the mixed solution for obtaining step (1) in the step (2) continues to stir after 10min-12h, is entering Row dried.Drying herein includes the drying of any one form of prior art, such as heat drying, forced air drying, vacuum It is dried, is spray-dried, microwave drying and centrifugal drying is all possible.
Soluble metal salt solution concentration is 0.001-10mol/L in the step (1), soluble phosphoric acid salt solution Concentration is 0.001-10mol/L.
Further, the mixed solution for obtaining step (1) in the step (2) continues to stir after 10min-12h, is entering Row dried.
Further, be incubated twice in the step (3) operation refer to successively 400-600 DEG C be incubated 2-8h, in 700- The operation of 1000 DEG C of insulation 3-36h.
The selection of the Parameter Conditions such as temperature, is conducive to the uniformity of clad in said method step；On the other hand because Clad sinters to be formed simultaneously with rich lithium material, increased the conjugation of clad and rich lithium material, improves the steady of clad It is qualitative；And clad can also occur interfacial reaction with the raw material of rich lithium material in sintering process, form conductivity higher Intermediate layer containing lithium (inter layer), so as to improve the ionic conductivity and chemical property of material.
The present invention positive effect be：The in-situ modification type structure of the present invention greatly improves the table of rich lithium material Face stability and electrical conductivity, charging and discharging capacity, efficiency, multiplying power and the cycle performance for making material is all significantly improved；This Invention preparation process is simple, and with low cost, as a result favorable reproducibility, is suitable to large-scale promotion.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis Spectrum.
Fig. 2 is the first charge-discharge curve comparison of the comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis Figure, in figure, curve 1 is comparative example 1, curve 2 is embodiment 1, and curve 3 is embodiment 2.
Fig. 3 is comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis under different electric current densities Discharge curve comparison diagram.
Fig. 4 is the cycle performance curve comparison of the comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis Figure.
Specific embodiment
The present invention is described in further detail below by specific embodiment.
Embodiment one：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad be metal phosphate, be specifically iron phosphate, the iron phosphate by diammonium phosphate, nine Liquid glauber salt acid is iron to be obtained, and the rich lithium material presoma is Ni0.13Co0.13Mn0.54O2With the mixture of Lithium hydrate, clad accounts for The mol ratio of raw material is 0.01%, and rich lithium material presoma is 99.99%, wherein, Li and Ni0.13Co0.13Mn0.54Mole Than for 1.5:1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1.5Mn0.54Ni0.13Co0.13O2- 0.0001FePO4。
The rich lithium material presoma can be obtained using prior art, and the side that prior art prepares rich lithium material may also be employed Method prepares the in-situ modification type richness lithium material coated with metal phosphate of above-described embodiment.
Embodiment two：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically manganese phosphate, and the manganese phosphate is by ammonium dihydrogen phosphate, vinegar Sour manganese is obtained, and the rich lithium material presoma is AlCr0.5The hydroxide of Mn and the mixture of lithium carbonate, clad mole It is 12% that amount accounts for raw material percentages, rich lithium material presoma 88%, AlCr0.5The mol ratio of Mn and Li is 1:2.5, obtain Surface in situ modification type richness lithium material chemical formula is 0.88Li2MnAlCr0.5O3-0.12LiMnPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
The design parameters such as the temperature for being adopted are can realize that obtaining final product is defined.
Embodiment three：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad be metal phosphate, be specifically nickel phosphate, the nickel phosphate by ammonium dihydrogen phosphate, six Water nickel nitrate is obtained, and the rich lithium material presoma is Mg0.13Mo0.13Mn0.54S0.2Carbonate and lithium acetate mixture, Li With Mg0.13Mo0.13Mn0.54S0.2Mol ratio is 1:1, it is 0.01% that the mole of clad accounts for the percentage ratio of raw material, rich lithium material Material precursor is 99.99%, and the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999LiMn0.54Mg0.13Mo0.13S0.2O1.8-0.0001LiNiPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 0.001mol/L, the soluble phosphoric acid of selection The concentration of saline solution is 0.001mo l/L；The mole of wherein soluble phosphate is 1 times of soluble metallic salt, solvable Property slaine and rich lithium material presoma mol ratio be 0.0001：0.9999.
(2) mixed solution for obtaining step (1) continues to stir 10min, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 2h at 600 DEG C successively, the operation of 3h is incubated at 1000 DEG C.
Example IV：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically C.I. Pigment Violet 14, and the C.I. Pigment Violet 14 is by sodium phosphate, six liquid glauber salt Sour cobalt is obtained, and the rich lithium material presoma is Ti0.13Zr0.13Mn0.54P0.1Oxalates and lithium nitrate mixture, clad Mole account for raw material 0.01%, remaining as rich lithium material presoma, wherein Li and Ti0.13Zr0.13Mn0.54P0.1Mol ratio is 1.2：1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1.2Mn0.54Ti0.13Zr0.13P0.1O2- 0.0001LiCoPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 10mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 10mol/L；The mole of soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt and richness Lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution for obtaining step (1) continues to stir 12h, then by mixed solution filtration washing, then is done Dry process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 8h at 400 DEG C successively, the operation of 36h is incubated at 700 DEG C.
Embodiment five：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically aluminum phosphate, and the aluminum phosphate is by potassium phosphate, aluminum nitrate It is obtained, the rich lithium material presoma is Fe0.1Ru0.1Mn0.54B0.1O2With the mixture of Lithium hydrate, clad accounts for raw material Molar percentage is 12%, remaining as rich lithium material presoma, wherein Li and Fe0.1Ru0.1Mn0.54B0.1Mol ratio be 1.5： 1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.88Li1.23Mn0.5Fe0.1Ru0.14B0.1O2-0.12AlPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 1mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 1mol/L；The mole of wherein soluble phosphate is 2 times of soluble metallic salt, soluble metallic salt with Rich lithium material presoma mol ratio is 0.12：0.88.
(2) mixed solution for obtaining step (1) continues to stir 1h, then by mixed solution filtration washing, then is done Dry process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 5h at 450 DEG C successively, the operation of 25h is incubated at 800 DEG C.
Embodiment six：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically zirconium phosphate, and the zirconium phosphate is by ammonium dihydrogen phosphate, different Propanol zirconium is obtained, and the rich lithium material presoma is Cu0.1Sn0.1Mn0.54F0.1O2With the mixture of Lithium hydrate, wherein Li with Cu0.1Sn0.1Mn0.54F0.1Mol ratio be 1.5：1, it is 0.01% that the mole of clad accounts for the percentage ratio of raw material, remaining as Rich lithium material presoma, obtain surface in situ modification type richness lithium material chemical formula be 0.9999Li1.23Mn0.54Cu0.1Sn0.1F0.1O2-0.0001LiZr0.5PO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 2mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 2mol/L；The mole of wherein soluble phosphate is 1 times of soluble metallic salt, soluble metallic salt with Rich lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution for obtaining step (1) continues to stir 1h, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 2h at 500 DEG C successively, the operation of 20h is incubated at 850 DEG C.
Embodiment seven：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically titanium phosphate, and the titanium phosphate is by phosphoric acid, the fourth of metatitanic acid four Ester is obtained, and the rich lithium material presoma is Ni0.10Co0.10Mn0.57O2With the mixture of Lithium hydrate, wherein Li with Ni0.10Co0.10Mn0.57Mol ratio is 1.3：1, it is 12% that the mole of clad accounts for the percentage ratio of raw material, remaining as rich lithium material Material precursor, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.88Li1.23Mn0.57Ni0.10Co0.10O2- 0.12Ti0.75PO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 3mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 3mol/L；The mole of wherein soluble phosphate is 1-3 times of soluble metallic salt, soluble metallic salt It is 0.12 with rich lithium material presoma mol ratio：0.88.
(2) mixed solution for obtaining step (1) continues to stir 2h, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 2h at 500 DEG C successively, the operation of 20h is incubated at 850 DEG C.
Embodiment eight：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically magnesium phosphate, and the magnesium phosphate is by diammonium phosphate, sulfur Sour magnesium is obtained, and the rich lithium material presoma is Ni0.30Mn0.48Fe0.08O2With the mixture of Lithium hydrate, the quality of clad The mass percent for accounting for raw material is 12%, remaining as rich lithium material presoma, wherein Li and Ni0.30Mn0.48Fe0.08Mole Than for 1.7：1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.88Li1。13Mn0.48Ni0.30Fe0.08O2- 0.12LiMgPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 4mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 4mol/L；The mole of wherein soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt with Rich lithium material presoma mol ratio is 0.12：0.88.
(2) mixed solution for obtaining step (1) continues to stir 6h, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 4h at 600 DEG C successively, the operation of 16h is incubated at 860 DEG C.
Embodiment nine：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically zinc phosphate, and the zinc phosphate is by potassium phosphate, zinc sulfate It is obtained, the rich lithium material presoma is Ni0.30Mn0.48Fe0.08O2With the mixture of Lithium hydrate, the mole of clad accounts for The percentage ratio of raw material is 0.01%, remaining as rich lithium material presoma, wherein Li and Ni0.30Mn0.48Fe0.08Mol ratio be 1.3：1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1。13Mn0.48Ni0.30Fe0.08O2- 0.0001LiZnPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 5mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 5mol/L；The mole of wherein soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt with Rich lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution that obtains step (1) continues to stir 6h, then by mixed solution filtration washing after, then carry out Dried；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 4h at 600 DEG C successively, the operation of 16h is incubated at 860 DEG C.
Embodiment ten：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness Lithium material presoma, the clad is metal phosphate, is specifically cupric phosphate, and the cupric phosphate is by ammonium phosphate, copper sulfate It is obtained, the rich lithium material presoma is Ni0.30Mn0.48Fe0.08O2With the mixture of Lithium hydrate, the mole of clad accounts for The matter percentage ratio of raw material is 0.01%, remaining as rich lithium material presoma, wherein Li and Ni0.30Mn0.48Fe0.08Mol ratio For 1.12：The 1 surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1。1Mn0.48Ni0.30Fe0.08O2- 0.00001CuPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma, Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 6mol/L, the soluble phosphoric acid salt of selection The concentration of solution is 6mol/L；The mole of wherein soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt with Rich lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution that obtains step (1) continues to stir 6h, then by mixed solution filtration washing after, then carry out Dried；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation Material, twice insulation operation refers to and be incubated 4h at 600 DEG C successively, the operation of 16h is incubated at 860 DEG C.
The following is the data of the test that the surface in situ modification type richness lithium material obtained to the present invention is carried out：
First, comparative example 1-3 is set, and comparative example 1-3 is the rich lithium material that prior art is obtained, comparative example 1：Step 1, Precursor synthesis
According to the ratio (Li of the amount of material:Ni:Co:Mn=1.24:0.13:0.13:0.54) nickel protoxide, oxidation are weighed Cobalt, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 3%, after mixing 12 hours in batch mixer, by solid content 20wt%'s Ratio adds deionized water, then pours slurry into grinding in ball grinder and is less than 0.3 micron to middle granularity.Finally by the slurry for obtaining Material is spray-dried, that is, obtain Li [Li0.20Ni0.13Co0.13Mn0.54]O2Presoma.
Step 2, high temperature sintering
Presoma is incubated 5 hours at 450 DEG C, then proceedes to be warmed up to 800 DEG C, is incubated 25 hours；Finally it is naturally cooling to Room temperature, that is, obtain Li [Li0.20Ni0.13Co0.13Mn0.54]O2Material.
Comparative example 2：Step 1, precursor synthesis
According to the ratio (Li of the amount of material:Ni:Co:Mn=1.27:0.10:0.10:0.57) nickel protoxide, oxidation are weighed Cobalt, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 3%, after mixing 12 hours in batch mixer, by solid content 20wt%'s Ratio adds deionized water, then pours slurry into grinding in ball grinder and is less than 0.3 micron to middle granularity.Finally by the slurry for obtaining Material is stirred to after doing in 60 DEG C of water-baths, is dried 12 hours in 100 DEG C of vacuum constant-temperature container, that is, obtain Li [Li0.23Ni0.10Co0.10Mn0.57]O2Presoma.
Step 2, high temperature sintering
Presoma is incubated 2 hours at 500 DEG C, then proceedes to be warmed up to 850 DEG C, is incubated 20 hours；Finally it is naturally cooling to Room temperature, that is, obtain Li [Li0.23Ni0.10Co0.10Mn0.57]O2Material.
Comparative example 3：Step 1, precursor synthesis
According to the ratio (Li of the amount of material:Ni:Fe:Mn=1.16:0.30:0.08:0.48) nickel protoxide, nitric acid are weighed Ferrum, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 3%, after mixing 12 hours in batch mixer, by solid content 20wt%'s Ratio adds deionized water, then pours slurry into grinding in ball grinder and is less than 0.3 micron to middle granularity.Finally by the slurry for obtaining Material is filtered, and fully after washing, is dried 6 hours in 100 DEG C of convection ovens, that is, obtain Li [Li0.13Ni0.30Mn0.48Fe0.08]O2's Presoma.
Step 2, high temperature sintering
Presoma is incubated 4 hours at 600 DEG C, then proceedes to be warmed up to 860 DEG C, is incubated 16 hours；Finally it is naturally cooling to Room temperature, that is, obtain Li [Li0.13Ni0.30Mn0.48Fe0.08]O2Material.
In order to test the chemical property of the material of embodiment of the present invention 1-10 and comparative example 1-3, by material obtained above Expect for positive electrode, to be assembled into button cell, carry out charge-discharge test, specific experiment step is as follows：
1) above-mentioned active material, conductive carbon black (Supper P) and Kynoar (PVDF) are pressed into 80:10:10 ratio Mixing, adds METHYLPYRROLIDONE (NMP) to make slurry, is evenly applied on aluminium foil, is cut into after drying a diameter of 1.4 centimetres of circular pole piece.
2) will be dried 12 hours in 120 degree of vacuum drying oven after above-mentioned pole piece roll-in, then in the handss full of argon In casing, with pour lithium slice as negative material, with 1mol/L LiPF6-EC+DEC+DMC, (volume ratio is 1:1:1) it is electrolyte, with Celgard2300 is barrier film, dresses up CR2032 type button cells.
3) the button experimental cell of assembling is carried out into charge-discharge test, the voltage range of discharge and recharge on charge-discharge test instrument For：2～4.8V, the electric current density for defining 200mA/g is 1C, and the discharge and recharge system of high rate performance test is：Successively with 0.1C, The electric current density constant current charge-discharge of 0.2C, 0.5C, 1C, 3C is each 3 weeks.Cycle performance test discharge and recharge system be：First in 2- 4.8V voltage ranges with the electric current density constant current charge-discharge 3 weeks of 0.1C, then in 2-4.6V voltage ranges with the electric current density of 1C Carry out constant current charge-discharge.
Experimental cell 0.1C first discharge specific capacities, 3C specific discharge capacities and the 200 weeks appearances prepared according to the method described above The test result of amount conservation rate is listed in table 1.
From the point of view of charge-discharge test result, the compound rich lithium material of the surface in situ of embodiment of the present invention 1-10 cladding with it is right Do not carry out surface coated rich lithium material in ratio to compare, the discharge capacity first of material, 3C discharge capacities and cycle performance are equal There is different degrees of raising.
The electrochemical property test tables of data of prepared material in the embodiment of the present invention of table 1 and comparative example
Fig. 1 is X ray diffracting spectrum (other specific embodiments of material prepared by comparative example 1, embodiment 1 and embodiment 2 The XRD spectrum of the material of preparation is similar, omits), the XRD figure of material is all α-NaFeO before and after as can be seen from the figure coating2Layer Shape structure, illustrates to coat the basic layer structure on rich lithium material without significantly impact, wherein can see in the figure after cladding To there is class Li3PO4The diffraction maximum of structure, illustrates there is class Li in the material for coating3PO4This structure, so as to be conducive to improve The electrical conductivity of material.
Fig. 2, Fig. 3 and Fig. 4 are respectively first charge-discharge comparison diagram, the multiplying power discharging of embodiment 1, embodiment 2 and comparative example 1 Capacity comparison figure and cycle performance comparison diagram.As can be seen from the figure the initial discharge of embodiment 1 and 2 is coated through surface in situ Capacity, high rate performance and circulation volume conservation rate are all significantly improved.
The compound rich lithium material specific capacity height of the surface in situ cladding that the present invention is provided, high rate performance and good cycle, Can be used as pure electric automobile, the power lithium-ion battery positive electrode of plug-in hybrid-power automobile.And prepare simply, hold Easy industrialized production.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair Change, equivalent, improvement etc., should be included within the scope of the present invention.

Claims (13)

1. a kind of surface in situ modification type richness lithium material, it is characterised in that raw material includes clad, rich lithium material presoma, The clad is metal phosphate, and rich lithium material presoma is in oxide, hydroxide, carbonate, the oxalates of MnMA At least one mixture with lithium source, wherein M is metallic element, and A is at least one in S, P, B and F.
2. in-situ modification type according to claim 1 richness lithium material, it is characterised in that the metal phosphate be Ti, Mg, At least one of Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni corresponding with Mo phosphate.
3. in-situ modification type according to claim 1 richness lithium material, it is characterised in that in the rich lithium material presoma Metal M is at least one in Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn.
4. in-situ modification type according to claim 1 richness lithium material, it is characterised in that the lithium source is Lithium hydrate, carbon At least one in sour lithium, lithium acetate, lithium nitrate, wherein Li are 1-2.5 with the mol ratio of MnMA：1.
5. in-situ modification type according to claim 1 richness lithium material, it is characterised in that clad mole in the raw material Amount percentage ratio is 0.01%-12%, and the mole percentage ratio of the rich lithium material presoma is 88%-99.99%.
6. in-situ modification type according to claim 1 richness lithium material, it is characterised in that the in-situ modification type richness lithium material Chemical formula be (1-a) Li1+xMnyMzAwOr-aLibMecPO4, wherein, 0.0001≤a≤0.12,0≤b≤3,0≤c≤1.5, 0 ＜ x≤1,0 ＜ y≤1,0≤z ＜ 1,0≤w≤0.2,1.8≤r≤3.
7. it is a kind of prepare described in claim 1-6 any one in-situ modification type richness lithium material method, it is characterised in that should Method is included in rich lithium material precursor particle and coats metal phosphate compounds, and then Jing high temperature sinterings form in-situ modification Type richness lithium material.
8. it is according to claim 7 prepare in-situ modification type richness lithium material method, it is characterised in that the method include as Lower step, (1) is added into soluble phosphate in rich lithium material presoma, while stirring Deca soluble metal salt solution, The mole of wherein soluble phosphate is 1-3 times of soluble metallic salt, and soluble metallic salt rubs with rich lithium material presoma You are than being 0.0001-0.12：0.9999-0.88.
(2) mixed solution for obtaining step (1) continues to stir, and is then dried process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation.
9. it is according to claim 8 prepare in-situ modification type richness lithium material method, it is characterised in that the step (1) Middle soluble phosphate includes at least one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, sodium phosphate, potassium phosphate.
10. it is according to claim 8 prepare in-situ modification type richness lithium material method, it is characterised in that the step (1) Middle soluble metallic salt is at least one in the soluble-salt of Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni and Mo.
11. methods for preparing in-situ modification type richness lithium material according to claim 8, it is characterised in that the step (1) Middle soluble metal salt solution concentration is 0.001-10mol/L, and the concentration of soluble phosphoric acid salt solution is 0.001-10mol/ L。
12. methods for preparing in-situ modification type richness lithium material according to claim 8, it is characterised in that the step (2) The middle mixed solution for obtaining step (1) continues to stir after 10min-12h, is being dried process.
13. methods for preparing in-situ modification type richness lithium material according to claim 8, it is characterised in that the step (3) In twice insulation operation refer to successively 400-600 DEG C be incubated 2-8h, 700-1000 DEG C be incubated 3-36h operation.
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CN109888248A (en) * 2019-03-26 2019-06-14 湖北锂诺新能源科技有限公司 Manganese phosphate coats the preparation method of rich oxidate for lithium positive electrode
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CN112542576A (en) * 2019-09-23 2021-03-23 荆门市格林美新材料有限公司 Coated LiFePO4Preparation method of Al-doped nickel-cobalt-manganese ternary cathode material of coating
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CN109888248A (en) * 2019-03-26 2019-06-14 湖北锂诺新能源科技有限公司 Manganese phosphate coats the preparation method of rich oxidate for lithium positive electrode
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