CN109148853A - A kind of dual cladding richness oxidate for lithium solid-solution material and preparation method thereof - Google Patents

A kind of dual cladding richness oxidate for lithium solid-solution material and preparation method thereof Download PDF

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CN109148853A
CN109148853A CN201810952063.5A CN201810952063A CN109148853A CN 109148853 A CN109148853 A CN 109148853A CN 201810952063 A CN201810952063 A CN 201810952063A CN 109148853 A CN109148853 A CN 109148853A
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amount
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nitrate
lithium
solution
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宋英杰
伏萍萍
徐宁
吴孟涛
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Chengdu Bamo Technology LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • H01M4/582—Halogenides
    • 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
    • H01M4/58—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 salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of dual cladding richness oxidate for lithium solid-solution materials and preparation method thereof, and solid-solution material is coated with phosphate and the double cladding of fluoride.Preparation method includes the following steps: that metal position yttrium orientation, which is prepared, by coprecipitation and high-temperature roasting technique first adulterates rich oxidate for lithium solid-solution material；Then metal phosphate/metal fluoride dual cladding is prepared by multiple step coprecipitation method and low-temperature bake technique, yttrium orientation in metal position adulterates rich oxidate for lithium solid-solution material.The present invention improves its structural stability by the orientation doping of metal position yttrium；Metal phosphate clad has the characteristics that stable structure, ionic conductivity are good, and metal fluoride clad has the characteristics that densification, and the design of dual cladding structure effectively inhibits reacting for surface and electrolyte.

Description

A kind of dual cladding richness oxidate for lithium solid-solution material and preparation method thereof
Technical field
The present invention relates to lithium ion secondary battery anode material field more particularly to a kind of dual cladding richness oxidate for lithium are solid Solution material and preparation method thereof.
Background technique
The key of popularization and application new-energy automobile is to realize its economy and the convenience used and conventional fuel oil automobile Quite.Current new-energy automobile, there are larger gap, promotes economy and ease of use is not compared with conventional fuel oil automobile Carry out the Main way of new-energy automobile development in significant period of time.
Power battery is the core of new-energy automobile, and wherein lithium ion battery has in terms of cost, energy density Apparent advantage, the convenience that will significantly promote new-energy automobile economy and use, in lithium-ion battery system just Pole material is deciding factor.New-energy automobile should be completely or partially using being driven by electricity, can compared with conventional fuel oil automobile Fuel consumption is reduced, but current new-energy automobile cannot still offset in the expense that Life cycle fuel consumption is saved and be increased The cost added.If pure electric automobile course continuation mileage reaches 400 kilometers, 1.0 yuan/Wh item below is reduced in battery system cost Under part, the economy in Life cycle can be close to conventional fuel oil automobile.The ease of use of new-energy automobile is promoted, is increased The course continuation mileage of pure electric drive traveling is crucial.To increase course continuation mileage, it is necessary to increase the energy for carrying electrokinetic cell system storage Amount, under the premise of not dramatically increasing newly energy vehicle weight and volume, it is necessary to improve the specific energy and energy density of power battery. If pure electric automobile course continuation mileage reaches 400 kilometers, electrokinetic cell system specific energy needs to be promoted to 250Wh/kg or so, monomer Battery specific energy need to promote 350Wh/kg.
Rich oxidate for lithium solid solution cathode material have the characteristics that specific capacity it is high, it is at low cost, have a safety feature, be a new generation Lithium-ion-power cell specific energy density reaches one of candidate positive electrode of most application prospect of 350Wh/kg target.It is based on The excellent properties of rich oxidate for lithium solid-solution material height ratio capacity high voltage, domestic many companies and research institution's last decade are all thrown Enter certain energy to study it.But there are still following problems for rich oxidate for lithium solid-solution material: 1, rich oxidate for lithium Due to the precipitation of oxygen in cyclic process, structure can change solid-solution material；2, under high voltage condition, product meeting and electricity Solution liquid reacts, and influences product structure stability.
In order to solve the problems, such as material structure stability, researchers have done a large amount of work, rich lithium in order to improve The stability of object solid-solution material need to guarantee the uniform mixing and progress element orientation doping of each element；In order to inhibit rich lithium The reaction of oxide solid solution material and electrolyte need to carry out fine and close cladding in rich oxidate for lithium material surface；In order to improve The high rate performance of rich oxidate for lithium solid-solution material need to increase the reactivity of solid liquid interface.But conventional coprecipitation is generally same When be added two kinds of substances of precipitating reagent and complexing agent, increase reaction controlling difficulty；Latter two designs to a certain extent again simultaneously In the presence of the relationship inhibited mutually, in order to increase the reactivity of solid liquid interface, solid-liquid contact area need to be increased, and contact area Increase the compactness it is difficult to ensure that clad.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of dual cladding richness oxidate for lithium solid-solution material and its systems Preparation Method improves its structural stability by the doping of metallic yttrium, pass through double-coating design and meanwhile improve material from The anticorrosive stability of subconductivity and material.
Technical scheme is as follows:
A kind of dual cladding richness oxidate for lithium solid-solution material, material are followed successively by core I, clad II and packet from inside to outside Coating III；Core I is the rich oxidate for lithium solid-solution material of metal doped yttrium, and clad II is metal fluoride clad, packet Coating III is metal phosphate clad.
A kind of preparation method of dual cladding richness oxidate for lithium solid-solution material, includes the following steps:
1) according to molecular formula LiaMnbNicCodYeO2Lithium source, manganese source, nickel source, cobalt source and yttrium source are weighed, deionized water is added It stirs evenly, obtains solidliquid mixture A, wherein 1.12≤a≤1.24,0.5≤b/ (b+c+d+e)≤0.7,0.1≤c/ (b+c+ D+e)≤0.3,0.1≤d/ (b+c+d+e)≤0.3,0.02≤e/ (b+c+d+e)≤0.05, a+b+c+d+e=2；
2) ammonium carbonate is added dropwise into the solution A, the time used is 4~8h, obtains solidliquid mixture B, wherein ammonium carbonate The amount of substance/(amount of manganese substance+nickel source substance amount+cobalt substance amount+yttrium substance amount)=(1.5~2): 1；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 200~260 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature be 850~950 DEG C, calcining time be 8~ 12h obtains material D；
5) the material D is added in deionized water, under agitation, ammonium fluoride and metal nitrate is added dropwise thereto I, time 4h~8h used obtain solidliquid mixture E, wherein amount=100 of I substance of amount/metal nitrate of material D substance: (0.5~1) is fluorinated amount=2:1 of I substance of amount/metal nitrate of ammoniacal substance；
6) the solidliquid mixture E is dry, drying temperature is 100~120 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature be 350~450 DEG C, calcining time be 2~ 6h obtains material G；
8) the material G is added in deionized water, under agitation, ammonium dihydrogen phosphate and metal nitre is added dropwise thereto Hydrochlorate II, time 4h~8h used, obtains solidliquid mixture H, wherein the amount of material G substance/metal nitrate substance amount= 100:(0.5~1), amount/metal nitrate substance amount=2:3 of ammonium dihydrogen phosphate substance；
9) the solidliquid mixture H is dry, drying temperature is 100~120 DEG C, obtains material J；
10) the material J is roasted in nitrogen atmosphere, maturing temperature be 350~450 DEG C, calcining time be 2~ 6h obtains material K；
11) the material K crushed, be sieved, packed and can obtain final products.
Further, the step 1) lithium source is lithium nitrate or lithium acetate.
Further, the step 1) manganese source is manganese nitrate or manganese acetate.
Further, the step 1) cobalt source is cobalt nitrate or cobalt acetate.
Further, the step 1) nickel source is nickel nitrate or nickel acetate.
Further, step 1) the yttrium source is yttrium nitrate.
Further, the step 5) metal nitrate I is cobalt nitrate or manganese nitrate.
Further, the step 8) metal nitrate II is nitric acid vanadium or Titanium Nitrate.
The present invention passes through coprecipitation first and high-temperature roasting technique is prepared metal position yttrium orientation and adulterates rich lithia Compound solid-solution material；Then metal phosphate/metal fluorine is prepared by multiple step coprecipitation method and low-temperature bake technique Compound dual cladding, metal position yttrium orientation adulterate rich oxidate for lithium solid-solution material.The present invention is by being added precipitating reagent complexing agent Substance-ammonium carbonate of one ensure that the uniform mixing and the orientation doping of metal position yttrium of each element, it is steady to improve its structure It is qualitative；By dual packet coating design, surface layer is the good metal phosphate clad of ionic conductivity, and inner layer is fine and close metal Fluoride clad not only inhibits reacting for surface and electrolyte, improves the stability of material, while passing through electric conductivity Enhancing also improves the high rate performance of product.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of dual cladding richness oxidate for lithium solid-solution material；
Fig. 2 is a kind of process flow chart of dual cladding richness oxidate for lithium solid-solution material preparation method.
Specific embodiment
Technical solution of the present invention is described in detail with reference to embodiments.
Embodiment 1
A kind of preparation method of dual cladding richness oxidate for lithium solid-solution material, includes the following steps:
1) according to molecular formula Li1.12Mn0.58Ni0.2Co0.182Y0.018O2Weigh lithium nitrate, manganese nitrate, nickel nitrate, cobalt nitrate And yttrium nitrate, deionized water is added and stirs evenly, obtains solidliquid mixture A, wherein the amount of the substance of manganese nitrate is 5.8mol；
2) ammonium carbonate is added dropwise into the solution A, the time used is 8h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount=1.32mol；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 200 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature is 850 DEG C, and calcining time 12h is obtained Material D；
5) the material D is added in deionized water, ammonium fluoride is added dropwise thereto and cobalt nitrate, time 4h used are obtained Solidliquid mixture E, wherein the amount of material D substance/cobalt nitrate substance amount=100:0.5, is fluorinated amount/cobalt nitrate object of ammoniacal substance Amount=2:1 of matter；
6) the solidliquid mixture E is dry, drying temperature is 100 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 350 DEG C, and calcining time 6h obtains object Expect G；
8) the material G is added in deionized water, thereto dropwise addition ammonium dihydrogen phosphate and nitric acid vanadium, time 4h used, Solidliquid mixture H is obtained, wherein the amount of material G substance/nitric acid vanadium substance amount=100:0.5, the amount of ammonium dihydrogen phosphate substance/ Amount=2:3 of nitric acid vanadium substance；
9) the solidliquid mixture H is dry, drying temperature is 100 DEG C, obtains material J；
10) the material J is roasted in nitrogen atmosphere, maturing temperature is 350 DEG C, and calcining time 6h is obtained Material K；
11) the material K crushed, be sieved, packed and can obtain final products.
Comparative example 1
1) according to molecular formula Li1.12Mn0.58Ni0.2Co0.182Y0.018O2Weigh lithium nitrate, manganese nitrate, nickel nitrate, cobalt nitrate And yttrium nitrate, deionized water is added and stirs evenly, obtains solidliquid mixture A, wherein the amount of the substance of manganese nitrate is 5.8mol；
2) ammonium carbonate is added dropwise into the solution A, the time used is 8h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount=1.32mol；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 200 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature is 850 DEG C, and calcining time 12h is obtained Material D；
5) the material D is added in deionized water, ammonium fluoride is added dropwise thereto and cobalt nitrate, time 4h used are obtained Solidliquid mixture E, wherein the amount of material D substance/cobalt nitrate substance amount=100:0.5, is fluorinated amount/cobalt nitrate object of ammoniacal substance Amount=2:1 of matter；
6) the solidliquid mixture E is dry, drying temperature is 100 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 350 DEG C, and calcining time 6h obtains object Expect G；
8) the material G crushed, be sieved, packed and can obtain final products.
Comparative example 2
1) according to molecular formula Li1.12Mn0.58Ni0.2Co0.182Y0.018O2Weigh lithium nitrate, manganese nitrate, nickel nitrate, cobalt nitrate And yttrium nitrate, deionized water is added and stirs evenly, obtains solidliquid mixture A, wherein the amount of the substance of manganese nitrate is 5.8mol；
2) ammonium carbonate is added dropwise into the solution A, the time used is 4h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount=1.32mol；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 260 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature is 950 DEG C, and calcining time 6h obtains object Expect D；
5) the material D is added in deionized water, thereto dropwise addition ammonium dihydrogen phosphate and nitric acid vanadium, time 4h used, Solidliquid mixture E is obtained, wherein the amount of material D substance/nitric acid vanadium substance amount=100:0.5, the amount of ammonium dihydrogen phosphate substance/ Amount=2:3 of nitric acid vanadium substance；
6) the solidliquid mixture E is dry, drying temperature is 100 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 350 DEG C, and calcining time 6h obtains object Expect G；
8) the material G crushed, be sieved, packed and can obtain final products.
Embodiment 2
A kind of preparation method of dual cladding richness oxidate for lithium solid-solution material, includes the following steps:
1) according to molecular formula Li1.12Mn0.58Ni0.2Co0.182Y0.018O2Weigh lithium acetate, manganese acetate, nickel acetate, cobalt acetate And yttrium nitrate, deionized water is added and stirs evenly, obtains solidliquid mixture A, wherein the amount of the substance of manganese nitrate is 5.8mol；
2) ammonium carbonate is added dropwise into the solution A, the time used is 8h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount=1.32mol；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 200 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature is 850 DEG C, and calcining time 12h is obtained Material D；
5) the material D is added in deionized water, ammonium fluoride is added dropwise thereto and cobalt nitrate, time 4h used are obtained Solidliquid mixture E, wherein the amount of material D substance/cobalt nitrate substance amount=100:1, is fluorinated amount/cobalt nitrate substance of ammoniacal substance Amount=2:1；
6) the solidliquid mixture E is dry, drying temperature is 120 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 450 DEG C, and calcining time 2h obtains object Expect G；
8) the material G is added in deionized water, thereto dropwise addition ammonium dihydrogen phosphate and nitric acid vanadium, time 4h used, Solidliquid mixture H is obtained, wherein the amount of material G substance/nitric acid vanadium substance amount=100:1, amount/nitre of ammonium dihydrogen phosphate substance Amount=2:3 of sour vanadium substance；
9) the solidliquid mixture H is dry, drying temperature is 120 DEG C, obtains material J；
10) the material J is roasted in nitrogen atmosphere, maturing temperature is 450 DEG C, and calcining time 2h is obtained Material K；
11) the material K crushed, be sieved, packed and can obtain final products.
Embodiment 3
A kind of preparation method of dual cladding richness oxidate for lithium solid-solution material, includes the following steps:
1) according to molecular formula Li1.24Mn0.502Ni0.10Co0.12Y0.038O2Weigh lithium nitrate, manganese nitrate, nickel nitrate, cobalt nitrate And yttrium nitrate, deionized water is added and stirs evenly, obtains solidliquid mixture A, wherein the amount of the substance of manganese nitrate is 5.02mol；
2) ammonium carbonate is added dropwise into the solution A, the time used is 8h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount=1.14mol；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 260 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature is 900 DEG C, and calcining time 12h is obtained Material D；
5) the material D is added in deionized water, ammonium fluoride is added dropwise thereto and cobalt nitrate, time 4h used are obtained Solidliquid mixture E, wherein the amount of material D substance/cobalt nitrate substance amount=100:1, is fluorinated amount/cobalt nitrate substance of ammoniacal substance Amount=2:1；
6) the solidliquid mixture E is dry, drying temperature is 100 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 400 DEG C, and calcining time 6h obtains object Expect G；
8) the material G is added in deionized water, thereto dropwise addition ammonium dihydrogen phosphate and nitric acid vanadium, time 4h used, Solidliquid mixture H is obtained, wherein the amount of material G substance/nitric acid vanadium substance amount=100:0.5, the amount of ammonium dihydrogen phosphate substance/ Amount=2:3 of nitric acid vanadium substance；
9) the solidliquid mixture H is dry, drying temperature is 100 DEG C, obtains material J；
10) the material J is roasted in nitrogen atmosphere, maturing temperature is 400 DEG C, and calcining time 6h is obtained Material K；
11) the material K crushed, be sieved, packed and can obtain final products.
Embodiment 4
A kind of preparation method of dual cladding richness oxidate for lithium solid-solution material, includes the following steps:
1) according to molecular formula Li1.24Mn0.502Ni0.10Co0.12Y0.038O2Weigh lithium acetate, manganese acetate, nickel acetate, cobalt acetate And yttrium nitrate, deionized water is added and stirs evenly, obtains solidliquid mixture A, wherein the amount of the substance of manganese nitrate is 5.02mol；
2) ammonium carbonate is added dropwise into the solution A, the time used is 8h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount=1.14mol；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 260 DEG C, obtains material C；
4) the material C is roasted in air atmosphere, maturing temperature is 900 DEG C, and calcining time 12h is obtained Material D；
5) the material D is added in deionized water, ammonium fluoride is added dropwise thereto and cobalt nitrate, time 4h used are obtained Solidliquid mixture E, wherein the amount of material D substance/cobalt nitrate substance amount=100:1, is fluorinated amount/cobalt nitrate substance of ammoniacal substance Amount=2:1；
6) the solidliquid mixture E is dry, drying temperature is 120 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 400 DEG C, and calcining time 2h obtains object Expect G；
8) the material G is added in deionized water, thereto dropwise addition ammonium dihydrogen phosphate and Titanium Nitrate, time 4h used, Solidliquid mixture H is obtained, wherein the amount of material G substance/nitric acid vanadium substance amount=100:1, amount/nitre of ammonium dihydrogen phosphate substance Amount=2:3 of sour vanadium substance；
9) the solidliquid mixture H is dry, drying temperature is 120 DEG C, obtains material J；
10) the material J is roasted in nitrogen atmosphere, maturing temperature is 400 DEG C, and calcining time 2h is obtained Material K；
11) the material K crushed, be sieved, packed and can obtain final products.
Experimental conditions:
Fig. 1 is the structural schematic diagram of rich oxidate for lithium solid-solution material prepared by the present invention.As seen from the figure, from inside to outside according to Secondary is core I, clad II and clad III；The core is the rich oxidate for lithium solid solution material of metal position yttrium orientation doping Material, clad II are fine and close metal fluoride clad, and clad III is the good metal phosphate clad of ionic conductivity.
Table 1 is listed to be made using lithium ion secondary battery anode material made from Examples 1 to 4 and comparative example 1~2 and be buckled The specific discharge capacity of circulation for the first time and coulombic efficiency of formula battery.
The test condition of button cell is LR 2032,0.1C, 2.0~4.9V, vs.Li+/ Li, the charging/discharging apparatus used For blue electric charge and discharge instrument.
1 charge-discharge property contrast table of table
Sample Specific discharge capacity/(mAh/g) Coulombic efficiency/% for the first time High rate performance (1C/0.1C)/%
Example 1 272.9 86.1 90.5
Comparative example 1 266.2 84.5 70.2
Comparative example 2 258.1 77.3 87.7
Example 2 273.3 86.6 89.2
Example 3 270.6 86.1 90.9
Example 4 271.4 86.0 88.6
As can be seen from the data in the table, the lithium cobalt solid-solution material first discharge specific capacity of richness produced by the present invention is basic 270mAh/g is reached, coulombic efficiency has reached 86% or more for the first time, has stronger application performance.When independent fluoride cladding High rate performance be obviously deteriorated, independent metal phosphate coat when for the first time coulombic efficiency be obviously deteriorated.Main cause is fluoride The compactness of clad is good, but interfacial reaction poor activity, therefore high rate performance is poor；The interfacial reaction of metal phosphate clad is living Property is big, but the compactness of clad is poor, can not effectively inhibit the reaction with electrolyte, therefore coulombic efficiency is lower for the first time.
Table 2 is listed to be made using lithium ion secondary battery anode material made from Examples 1 to 4 and comparative example 1~2 The cycle performance of 053048 actual effect battery.The test condition of actual effect battery is filled for 0.5C, and 0.5C is put, 2.0~4.6V, and what is used fills Discharge equipment is blue electric charge and discharge instrument.
2. actual effect cycle performance of battery of table
Sample 400 circulation volume conservation rate/%
Example 1 82.5
Comparative example 1 76.1
Comparative example 2 67.7
Example 2 85.6
Example 3 84.3
Example 4 86.2
As can be seen from the data in the table, richness oxidate for lithium solid-solution material prepared by the present invention has good cyclicity Can, 400 times circulation volume conservation rate has reached 85% or more；Independent metal fluoride cladding or individually metal phosphate, which coat, to follow Ring performance is obviously deteriorated.Although main cause is that the interfacial reaction activity of metal phosphate clad is big, the cause of clad Close property is poor, can not effectively inhibit the reaction with electrolyte；Although fluoride clad compactness is preferable, due to reactivity Lower, electrode polarization increases as the cycle progresses, and cycle performance is caused to be deteriorated.
In conclusion the contents of the present invention are not limited in the above embodiments, the knowledgeable people in same area can Can propose other embodiments easily within technological guidance's thought of the invention, but this embodiment is included in this hair Within the scope of bright.

Claims (10)

1. a kind of dual cladding richness oxidate for lithium solid-solution material, it is characterised in that: the material is followed successively by core from inside to outside I, clad II and clad III；The core I is the rich oxidate for lithium solid-solution material of metal doped yttrium, the clad II For metal fluoride clad, the clad III is metal phosphate clad.
2. a kind of preparation method of dual cladding richness oxidate for lithium solid-solution material, it is characterised in that include the following steps:
1) according to molecular formula LiaMnbNicCodYeO2Lithium source, manganese source, nickel source, cobalt source and yttrium source are weighed, deionized water stirring is added Uniformly, solution A is obtained, wherein 1.12≤a≤1.24,0.5≤b/ (b+c+d+e)≤0.7,0.1≤c/ (b+c+d+e)≤0.3, 0.1≤d/ (b+c+d+e)≤0.3,0.02≤e/ (b+c+d+e)≤0.05, a+b+c+d+e=2；
2) ammonium carbonate is added dropwise into the solution A, time for adding is 4~8h, obtains solidliquid mixture B, wherein ammonium carbonate substance Amount/(amount of manganese substance+nickel substance amount+cobalt substance amount+yttrium substance amount)=(1.5~2): 1；
3) the solidliquid mixture B is spray-dried, spray drying temperature is 200~260 DEG C, obtains material C；
4) the material C being roasted in air atmosphere, maturing temperature is 850~950 DEG C, and calcining time is 8~12h, Obtain material D；
5) the material D is added in deionized water, thereto dropwise addition ammonium fluoride and metal nitrate I, time for adding 4h~8h, Solidliquid mixture E is obtained, wherein amount=100:(0.5~1 of I substance of amount/metal nitrate of material D substance), ammonium fluoride object Amount=2:1 of I substance of amount/metal nitrate of matter；
6) the solidliquid mixture E is spray-dried, drying temperature is 100~120 DEG C, obtains material F；
7) the material F is roasted in nitrogen atmosphere, maturing temperature is 350~450 DEG C, and calcining time is 2~6h, is obtained To material G；
8) the material G is added in deionized water, ammonium dihydrogen phosphate and metal nitrate II, time for adding 4h is added dropwise thereto ~8h obtains solidliquid mixture H, wherein amount=100:(0.5~1 of II substance of amount/metal nitrate of material G substance), phosphorus Amount=2:3 of II substance of amount/metal nitrate of acid dihydride ammonium substance；
9) the solidliquid mixture H is spray-dried, drying temperature is 100~120 DEG C, obtains material J；
10) the material J being roasted in nitrogen atmosphere, maturing temperature is 350~450 DEG C, and calcining time is 2~6h, Obtain material K；
11) the material K crushed, be sieved, packed and can obtain final products.
3. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 1) lithium source described in is lithium nitrate or lithium acetate.
4. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 1) manganese source described in is manganese nitrate or manganese acetate.
5. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 1) nickel source described in is nickel nitrate or nickel acetate.
6. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 1) cobalt source described in is cobalt nitrate or cobalt acetate.
7. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 1) yttrium source described in is yttrium nitrate.
8. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 5) metal nitrate I described in is cobalt nitrate or manganese nitrate.
9. the preparation method of dual cladding richness oxidate for lithium solid-solution material according to claim 2, it is characterised in that: step 8) metal nitrate II described in is nitric acid vanadium or Titanium Nitrate.
10. according to the dual cladding richness oxidate for lithium solid-solution material of the described in any item method preparations of claim 2-9 in lithium Application in ion battery.
CN201810952063.5A 2018-08-21 2018-08-21 A kind of dual cladding richness oxidate for lithium solid-solution material and preparation method thereof Pending CN109148853A (en)

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