CN110137489A - Nickel-cobalt lithium manganate material, preparation method and application with trace metal impurity - Google Patents

Nickel-cobalt lithium manganate material, preparation method and application with trace metal impurity Download PDF

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CN110137489A
CN110137489A CN201910533963.0A CN201910533963A CN110137489A CN 110137489 A CN110137489 A CN 110137489A CN 201910533963 A CN201910533963 A CN 201910533963A CN 110137489 A CN110137489 A CN 110137489A
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lithium manganate
cobalt lithium
nickel
metal
impurity
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CN110137489B (en
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王静任
曾雷英
魏国祯
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Xiamen Xiamen Tungsten New Energy Material Co Ltd
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Xiamen Xiamen Tungsten New Energy Material Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts 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

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Abstract

A kind of preparation method of the nickel-cobalt lithium manganate material with trace metal impurity, comprising the following steps: provide nickle cobalt lithium manganate sintering feed, the nickle cobalt lithium manganate sintering feed includes metal impurities；Metal chloride solutions are provided, ammonium hydroxide is added in Xiang Suoshu metal chloride solutions, so that complex reaction, which occurs, for the metal chloride in the metal chloride solutions and the ammonium hydroxide forms alkaline etch bath；And the nickle cobalt lithium manganate sintering feed and the alkaline etch bath are mixed, so that the alkaline etch bath is etched the metal impurities in the nickle cobalt lithium manganate sintering feed, obtain the nickel-cobalt lithium manganate material with trace metal impurity.The present invention also provides a kind of nickel-cobalt lithium manganate material and lithium ion battery with trace metal impurity.Preparation method provided by the present invention is simple, easy to operate, can not only remove magnetic impurity, moreover it is possible to remove non-magnetic impurity.

Description

Nickel-cobalt lithium manganate material, preparation method and application with trace metal impurity
Technical field
The present invention relates to a kind of preparation methods of anode material for lithium-ion batteries, more particularly to one kind to have trace metal miscellaneous The nickel-cobalt lithium manganate material of matter, preparation method and application.
Background technique
Lithium ion battery electrode material brings metal impurities into due to metal equipment abrasion and raw material etc. during the preparation process, These metal impurities main components are copper, iron, chromium, zinc, they can be dissolved during the charging process, then form simple substance, elemental copper, Iron, chromium, the nucleus of zinc are larger, the growth of special crystal quickly, so be easy to form dendrite in cathode, dendrite be easy to puncture every Film causes internal short-circuit of battery, leads to self-discharge of battery, even on fire, explosion.Therefore, the production of lithium ion battery electrode material The control of quality especially metal impurities is the key that improve lithium ion battery safety performance.It is currently used to remove metal impurities Method be that magnetic machine is removed using electromagnetism, principle be by magnetic substance excitation except magnetic foreign body equipment is by powder body material or liquid Have magnetic metal impurities absorption in body, demagnetization then is carried out to magnetic substance, magnetic foreign body is rinsed to discharge from magnetic substance Magnetic foreign body.In addition, the material of magnetic substance is mainly stainless steel material, during handling material, with material properties Change, long-time service may cause to corrode to equipment material, it is difficult to ensure that material removes magnetic metal impurity effect；Secondly, Electromagnetism is except calorific value is big in the magnetic machine course of work, energy consumption is higher, in type selecting because partial material characteristic is restricted；Most Afterwards, do not have magnetic or magnetic lower metal impurities except magnetic machine can not effectively remove by electromagnetism.
Summary of the invention
In view of this, it is necessary to provide the nickel-cobalt lithium manganate materials that a kind of preparation method simply has trace metal impurity Preparation method.
In addition, there is a need to provide a kind of nickel-cobalt lithium manganate material with trace metal impurity.
In addition, there is a need to provide a kind of lithium ion battery.
A kind of preparation method of the nickel-cobalt lithium manganate material with trace metal impurity, comprising the following steps:
Nickle cobalt lithium manganate sintering feed is provided, the nickle cobalt lithium manganate sintering feed includes metal impurities；
Metal chloride solutions are provided, ammonium hydroxide are added in Xiang Suoshu metal chloride solutions, so that the metal chloride Metal chloride and the ammonium hydroxide in solution occur complex reaction and form alkaline etch bath；And
The nickle cobalt lithium manganate sintering feed and the alkaline etch bath are mixed, so that the alkaline etch bath is to the nickel cobalt Metal impurities in LiMn2O4 sintering feed are etched, and obtain the nickel-cobalt lithium manganate material with trace metal impurity.
Further, the chemical formula of the metal chloride is MCld, wherein M include in copper, iron, chromium and zinc at least One kind, 2≤d≤3；The concentration of metal chloride described in the metal chloride solutions is 0.01mol/L~0.1mol/L.
Further, the alkaline etch bath includes M (NH3)2dCld, the M (NH3)2dCldMole be greater than or equal to The mole of the metal impurities.
Further, the pH of the alkaline etch bath is 9~12.
Further, the metal impurities include transition metal, the metal ion in the metal chloride and the mistake It crosses metal and belongs to same element.
Further, the metal impurities include at least one of copper, iron, chromium and zinc.
Further, the chemical formula of the nickle cobalt lithium manganate sintering feed is LizNixCoyMn1-x-yO2, wherein 1≤z≤ 1.05,0≤x≤1,0≤y≤1,0≤x+y≤1.
Further, the nickle cobalt lithium manganate sintering feed after lithium salts and transition metal oxide sintering by obtaining；It is described Lithium salts includes at least one of lithium carbonate or lithium hydroxide, and the chemical formula of the transition metal oxide meets NiaCobMn1-a-b (OH)2Or NiaCobMn1-a-bCO3At least one of, wherein 0≤a≤1,0≤b≤1,0≤a+b≤1.
Further, the temperature of the sintering is 850 DEG C~950 DEG C；The atmosphere of the sintering is air atmosphere, oxygen gas Atmosphere or air oxygen gaseous mixture, the oxygen concentration in air oxygen gaseous mixture is between 20%~100%.
It further, further include washing step after etching reaction occurs, the washing step includes:
By the nickle cobalt lithium manganate sintering feed filtering after generation etching reaction, filter cake is obtained；And
The filter cake is washed, filtered, dried, is sieved, the nickel cobalt mangaic acid with trace metal impurity is obtained Lithium material.
A kind of nickel-cobalt lithium manganate material with trace metal impurity, the nickle cobalt lithium manganate with trace metal impurity Obtained by the preparation method of nickel-cobalt lithium manganate material described in material with trace metal impurity.
Further, the nickel-cobalt lithium manganate material of the trace metal impurity includes nickle cobalt lithium manganate and metal impurities, institute It states metal impurities to be doped in the nickle cobalt lithium manganate, the metal impurities include copper, and the content of the copper is lower than 30ppb.
Further, the metal impurities also include zinc and chromium, and the content of the zinc is lower than 30ppb, the content of the chromium Lower than 40ppb.
Further, the total content of the metal impurities is lower than 100ppb.
A kind of lithium ion battery, the lithium ion battery include the nickle cobalt lithium manganate material with trace metal impurity Material.
The preparation method of metal impurities in removal nickel-cobalt lithium manganate material provided by the present invention passes through addition and nickel cobalt The corresponding metal chloride of metal impurities in LiMn2O4 sintering feed, and in conjunction with ammonium hydroxide, there is specific aim and efficiently go Except metal impurities；Meanwhile by the preparation method, the magnetic impurities such as iron can not only be removed, moreover it is possible to remove copper removal, chromium, zinc etc. Non-magnetic impurity；And preparation method is simple, easy to operate, to prepare high safety performance, nickel with trace metal impurity Cobalt lithium manganate material electrode material, for realizing the production of power-type lithium ion battery electrode material, new-energy automobile being promoted to produce The problems such as industry develops, has important practical significance.
Detailed description of the invention
Fig. 1 is the preparation method process of the metal impurities in removal nickel-cobalt lithium manganate material provided in an embodiment of the present invention Figure.
Fig. 2A is the open-circuit voltage test chart that the button cell of 1-3 of embodiment of the present invention preparation is shelved one week；Fig. 2 B is this The button cell of inventive embodiments 4-6 preparation shelves one week open-circuit voltage test chart；Fig. 2 C is the button of comparative example 1-3 preparation Battery shelves one week open-circuit voltage test chart.
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
To better understand the objects, features and advantages of the present invention, with reference to the accompanying drawing and specific real Applying mode, the present invention will be described in detail.It should be noted that in the absence of conflict, presently filed embodiment and reality The feature applied in mode can be combined with each other.Many details are explained in the following description in order to fully understand this hair Bright, described embodiment is only some embodiments of the invention, rather than whole embodiments.Based on the present invention In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts Mode shall fall within the protection scope of the present invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more All and arbitrary combinations of relevant listed item.
Referring to Fig. 1, the embodiment of the present invention provides a kind of preparation of nickel-cobalt lithium manganate material with trace metal impurity Method, comprising the following steps:
Step S1: nickle cobalt lithium manganate sintering feed is provided, the nickle cobalt lithium manganate sintering feed includes metal impurities；
Step S2: metal chloride solutions are provided, ammonium hydroxide are added in Xiang Suoshu metal chloride solutions, so that the metal Metal chloride and the ammonium hydroxide in chloride solution occur complex reaction and form alkaline etch bath；
Step S3: mixing the nickle cobalt lithium manganate sintering feed and the alkaline etch bath, so that the alkaline etch bath pair Metal impurities in the nickle cobalt lithium manganate sintering feed are etched, and obtain the nickle cobalt lithium manganate with trace metal impurity Material.
It in step sl, include nickle cobalt lithium manganate, the chemistry of the nickle cobalt lithium manganate in the nickle cobalt lithium manganate sintering feed Formula is LizNixCoyMn1-x-yO2, wherein 1≤z≤1.05,0≤x≤1,0≤y≤1,0≤x+y≤1.
The nickle cobalt lithium manganate sintering feed after lithium salts and transition metal oxide sintering by obtaining.The lithium salts includes carbon The chemical formula of at least one of sour lithium or lithium hydroxide, the transition metal oxide meets NiaCobMn1-a-b(OH)2Or NiaCobMn1-a-bCO3At least one of, wherein 0≤a≤1,0≤b≤1,0≤a+b≤1.The nickle cobalt lithium manganate sintering feed In include at least a kind of metal impurities, such as include at least one of transition metal such as copper, iron, chromium, zinc.
Further, the temperature of the sintering is 850 DEG C~950 DEG C, and sintering carries out in high temperature roller furnace；The sintering Atmosphere be air atmosphere, oxygen atmosphere or air oxygen gaseous mixture, air oxygen gaseous mixture oxygen concentration 20%~100% it Between.
In step s 2, the concentration of metal chloride is 0.01mol/L~0.1mol/L in the metal chloride solutions, The chemical formula of the metal chloride is MCld, wherein M is one of transition metal element, for example, M include copper, iron, chromium with And at least one of zinc, 2≤d≤3.
The equation of complex reaction occurs for the metal chloride and ammonium hydroxide are as follows:
MCld+2d NH3→M(NH3)2dCld。
Further, the pH of the alkaline etch bath is 9~12.
Further, the metal chloride MCldIn metal ions M and nickle cobalt lithium manganate sintering feed in metal impurities In transition metal belong to a kind of element.
In step s3, the metal impurities in the nickle cobalt lithium manganate sintering feed are mixed with the alkaline etch bath, described M (NH in metal impurities and the alkaline etch bath3)2dCldReaction generates solable matter, to be sintered from nickle cobalt lithium manganate It is removed in material, obtains the nickel-cobalt lithium manganate material with trace metal impurity.M (NH in alkaline etch bath3)2dCldMetal from When sub- M is identical as the transition metal element of metal impurities, the metal impurities and M (NH3)2dCldThe reaction equation etched Are as follows:
M(NH3)2dCld+M→2M(NH3)dCld/2。
Further, the M (NH in the alkaline etch bath3)2dCldMole is greater than or equal to the nickle cobalt lithium manganate material The mole of the metal impurities contained is expected, to guarantee that metal impurities are sufficiently removed.
M (NH in the preferably described alkaline etch bath3)2dCldMole is the nickel cobalt manganese metal impurities mole 106~107Times.
It further, further include washing step after etching reaction occurs, the washing step includes:
Step S31: the nickle cobalt lithium manganate sintering feed after generation etching reaction is filtered, filter cake is obtained；
Step S32: the filter cake is washed, is filtered, is dried, is sieved and etc., it obtains described with trace metal The nickel-cobalt lithium manganate material of impurity.
In step S31, filter cloth material used in the filter process is one in polypropylene fibre, polyvinyl and nylon Kind.
In step s 32, the washing includes the solution for being greater than or equal to the nickel-cobalt lithium manganate cathode material with quality Nickel-cobalt lithium manganate cathode material after etching reaction occurs for dispersion, and at the uniform velocity stirs at least 1 hour.The solution can be distilled water Or alkaline etch bath.
Further, at 150 DEG C, drying time 12h, drying carries out the drying temperature in vacuum drying oven；Institute It is nylon screen, 300 mesh of sieve mesh number that sieving, which is stated, using sieve.
The embodiment of the present invention also provides a kind of nickel cobalt manganese as prepared by the preparation method with trace metal impurity Sour lithium material, the nickel-cobalt lithium manganate material with trace metal impurity include nickle cobalt lithium manganate and metal impurities, the gold Belong to impurity to be doped in the nickle cobalt lithium manganate, the metal impurities include copper, and the content of the copper is lower than 30ppb.
Preferably, the content of the copper is lower than 10ppb, and in one embodiment, the content of the copper is 4ppb.
Further, the metal impurities also include chromium, and the content of the chromium is lower than 40ppb.
Preferably, the content of the chromium is lower than 10ppb, and in one embodiment, the content of the chromium is 4ppb.
Further, the metal impurities also include zinc, and the content of the zinc is lower than 30ppb.
Preferably, the content of the zinc is lower than 10ppb, and in one embodiment, the content of the zinc is 3ppb.
Further, the metal impurities also include iron, and the content of the iron is lower than 40ppb.
Preferably, the content of the iron is lower than 10ppb, and in one embodiment, the content of the chromium is 3ppb.
Further, the total content of the metal impurities is lower than 100ppb.
Preferably, the total content of the metal impurities is lower than 40ppb, in one embodiment, the metal impurities Total content is 17ppb.
The embodiment of the present invention also provides a kind of lithium ion battery, and the lithium ion battery includes electrode slice and is set to Diaphragm and electrolyte between electrode slice, the electrode slice include the nickel-cobalt lithium manganate material with trace metal impurity, Binder, conductive agent and collector, the nickel-cobalt lithium manganate material with trace metal impurity, binder and conductive agent are uniform It is coated on the collector after mixing.
The present invention is specifically described below by embodiment.
Embodiment 1
It is lithium salts and Ni by lithium carbonate1/3Co1/3Mn1/3(OH)2It is uniformly mixed for transition metal oxide in ball mill mixing machine After obtain mixing, wherein in the mixing lithium carbonate lithium atom (Li) and Ni1/3Co1/3Mn1/3(OH)2Middle metallic atom (Ni, Co and Mn) total content molar ratio be 1.05:1；The mixing is sintered, sintering temperature is 920 DEG C, 12 hours are kept the temperature, Sintering atmosphere is air；Machine is broken using Hubei Province or sintering block that twin rollers coarse crushing sinters, then use Mechanical Crushing, obtains nickel Cobalt lithium manganate material.
Prepare CuCl2Solution, Xiang Suoshu CuCl2Ammonium hydroxide, the CuCl are added in solution2It is anti-that complexing occurs for solution and ammonium hydroxide It answers: CuCl2+4NH3→Cu(NH3)4Cl2, form Cu (NH3)4Cl2Alkaline etching liquid, the CuCl2The molar concentration of solution is 0.01mol/L, the pH of the alkaline etch bath are 9.
The nickle cobalt lithium manganate sintering feed is added to containing Cu (NH3)4Cl2Alkaline etch bath in stir, the alkalinity The quality of etching liquid is three times of the nickle cobalt lithium manganate sintering feed, stirring 1h filtering, the nickle cobalt lithium manganate filter after being etched Cake；The nickle cobalt lithium manganate filter cake is dispersed in after stirring 1h in distilled water and is filtered, obtains the nickel cobalt containing trace metal impurity The nickle cobalt lithium manganate filter cake is put into vacuum drying oven and dries by LiMn2O4 filter cake, and setting drying temperature is 150 DEG C, even Continuous drying 12h, obtains the nickel-cobalt lithium manganate material powder of trace metal impurity.
Embodiment 2
Unlike the first embodiment: the transition metal oxide is Ni0.4Co0.3Mn0.3(OH)2；The lithium of lithium carbonate is former Son and Ni0.4Co0.3Mn0.3(OH)2The molar ratio of middle metallic atom total content is 1.04:1；Sintering temperature is 910 DEG C.
Prepare CrCl3Solution, Xiang Suoshu CrCl3Ammonium hydroxide, the CrCl are added in solution3It is anti-that complexing occurs for solution and ammonium hydroxide It answers: CrCl3+4NH3→Cr(NH3)4Cl3, form Cr (NH3)4Cl3Alkaline etching liquid, the Cr (NH3)4Cl3Solution it is mole dense Degree is 0.015mol/L, and the pH of the alkaline etch bath is 10.
Other steps are same as Example 1, are not repeated herein.
Embodiment 3
Unlike the first embodiment: the transition metal oxide is Ni0.5Co0.2Mn0.3(OH)2；The lithium of lithium carbonate is former Son and Ni0.5Co0.2Mn0.3(OH)2The molar ratio of middle metallic atom total content is 1.03:1；Sintering temperature is 900 DEG C.
Prepare CuCl2And CrCl3Mixed solution, Xiang Suoshu CuCl2And CrCl3Ammonium hydroxide, the CuCl are added in mixed solution2 And CrCl3Complex reaction: CuCl occurs with ammonium hydroxide2+4NH3→Cu(NH3)4Cl2, CrCl3+4NH3→Cr(NH3)4Cl3, formation contains There is Cu (NH3)4Cl2With Cr (NH3)4Cl3Alkaline etching liquid, Cu (NH in the alkaline etching liquid3)4Cl2With Cr (NH3)4Cl3's Molar concentration is 0.01mol/L, and the pH of the alkaline etch bath is 10.
Other steps are same as Example 1, are not repeated herein.
Embodiment 4
Unlike the first embodiment: the lithium salts is lithium hydroxide, and the transition metal oxide is Ni0.6Co0.2Mn0.2 (OH)2, the molar ratio of lithium atom and metallic atom total content is 1.02:1；Sintering temperature is 890 DEG C, and the atmosphere of sintering is to be passed through The air oxygen gaseous mixture that oxygen concentration is 60%.
Prepare ZnCl2And FeCl3Mixed solution, Xiang Suoshu ZnCl2And FeCl3Ammonium hydroxide, the ZnCl are added in mixed solution2 And FeCl3Complex reaction: ZnCl occurs with ammonium hydroxide2+4NH3→Zn(NH3)4Cl2, FeCl3+4NH3→Fe(NH3)4Cl3, formation contains There is Zn (NH3)4Cl2With Fe (NH3)4Cl3Alkaline etching liquid, the Zn (NH in the alkaline etching liquid3)4Cl2With Fe (NH3)4Cl3 Molar concentration be 0.02mol/L, the pH of the alkaline etch bath is 10.
Other steps are same as Example 1, are not repeated herein.
Embodiment 5
Unlike the first embodiment: the lithium salts is lithium hydroxide, and the transition metal oxide is Ni0.7Co0.1Mn0.2 (OH)2, the molar ratio of lithium atom and metallic atom total content is 1.01:1；Sintering temperature is 880 DEG C, and the atmosphere of sintering is to be passed through The air oxygen gaseous mixture that oxygen concentration is 80%.
Prepare CuCl2、CrCl3And ZnCl2Mixed solution, Xiang Suoshu CuCl2、CrCl3And ZnCl2Ammonia is added in mixed solution Water, the CuCl2、CrCl3And ZnCl2Complex reaction: CuCl occurs with ammonium hydroxide2+4NH3→Cu(NH3)4Cl2、CrCl3+4NH3→ Cr(NH3)4Cl3、ZnCl2+4NH3→Zn(NH3)4Cl2, formed and contain Cu (NH3)4Cl2、Cr(NH3)4Cl3With Zn (NH3)4Cl2's Alkaline etching liquid is put into Cu (NH in the alkaline etching liquid3)4Cl2、Cr(NH3)4Cl3With Zn (NH3)4Cl2Molar concentration it is equal It is 10 for 0.01mol/L, the alkaline etching liquid pH.
Other steps are same as Example 1, are not repeated herein.
Embodiment 6
Unlike the first embodiment: the lithium salts is lithium hydroxide, and the transition metal oxide is Ni0.8Co0.1Mn0.1 (OH)2, the molar ratio of lithium atom and metallic atom total content is 1:1；Sintering temperature is 850 DEG C, and the atmosphere of sintering is oxygen.
Prepare CuCl2、FeCl3、CrCl3And ZnCl2Mixed solution, Xiang Suoshu CuCl2、FeCl3、CrCl3And ZnCl2Mixing Ammonium hydroxide, the CuCl is added in solution2、FeCl3、CrCl3And ZnCl2Complex reaction: CuCl occurs with ammonium hydroxide2+4NH3→Cu(NH3)4Cl2、FeCl3+4NH3→Fe(NH3)4Cl3、CrCl3+4NH3→Cr(NH3)4Cl3、ZnCl2+4NH3→Zn(NH3)4Cl2, formation contains There is Cu (NH3)4Cl2、Fe(NH3)4Cl3、Cr(NH3)4Cl3With Zn (NH3)4Cl2Alkaline etching liquid, in the alkaline etching liquid Cu(NH3)4Cl2、Fe(NH3)4Cl3、Cr(NH3)4Cl3With Zn (NH3)4Cl2Molar concentration be 0.02mol/L, the alkalinity Etching solution pH is 10.
Other steps are same as Example 1, are not repeated herein.
Comparative example 1
With no treatment by the nickle cobalt lithium manganate sintering feed obtained in embodiment 6 through oversintering and crushing.
Other steps are same as Example 6, are not repeated herein.
Comparative example 2
The nickle cobalt lithium manganate sintering feed obtained in embodiment through oversintering and crushing is washed and dried by single flash.
Other steps are same as Example 6, are not repeated herein.
Comparative example 3
The nickle cobalt lithium manganate sintering feed obtained in embodiment through oversintering and crushing is washed and dried by distillation twice.
Other steps are same as Example 6, are not repeated herein.
The specific treatment conditions of embodiment 1-6 and comparative example 1-3 as shown in table 1 and table 2, wherein table 1 be embodiment 1-6 and Comparative example 1-3 provides the specific treatment conditions of nickel-cobalt lithium manganate material, and table 2 is to provide the specific treatment conditions of alkaline etch bath.
1 embodiment 1-6 of table and the specific treatment conditions of comparative example 1-3
2 embodiment 1-6 of table and the specific treatment conditions of comparative example 1-3
Inductive coupling is used to the nickle cobalt lithium manganate containing trace metal impurity prepared by embodiment 1-6 and comparative example 1-3 Plasma spectrum generator tests the surplus for the impurity that it contains, and the impurity includes Cu, Fe, Cr, Zn, please join table 3, to implement The impurity test result of the nickle cobalt lithium manganate containing trace metal impurity of example 1-6 and comparative example 1-3 preparation.
3 embodiment 1-6 of table and comparative example 1-3 impurity test result
From the test result of comparative example 1~3 can be seen that by simple distilled water wash and repeatedly washing and could not be effective Reduce the metal impurities in material.It can be seen that from the test result of Examples 1 to 6 through corresponding metal alkaline etching liquid Etching after, the content of respective metal impurity significantly reduces, and the content of the respective metal impurity is lower than 10ppb, embodiment 1, 2,3 impurity metal content arrived the level lower than 1,2,3 half of comparative example, and the total metal contents in soil of embodiment 6 is reduced to 14ppb, and not only the content of the magnetic impurities such as iron is effectively reduced in embodiment 6, while the non-magnetic impurities such as copper, chromium, zinc also have Effect reduces.
Positive material is used as to the nickle cobalt lithium manganate for containing trace metal impurity prepared by Examples 1 to 6 and comparative example 1~3 Material is assembled into button cell each 100, carries out burn-in test to the button cell respectively, i.e., charges to the button cell Then 4.2V shelves the open-circuit voltage for testing the button cell after a week.
It please refers to Fig. 2A, Fig. 2 B and Fig. 2 C, Fig. 2A is the open-circuit voltage test that the button cell of embodiment 1-3 is shelved one week Figure, Fig. 2 B are the open-circuit voltage test chart that the button cell of embodiment 4-6 is shelved one week, the button electricity that Fig. 2 C is comparative example 1-3 Shelve one week open-circuit voltage test chart in pond.As can be seen from Figure 2A, Examples 1 to 3 preparation containing trace metal impurity Nickle cobalt lithium manganate as positive electrode button cell there are certain self discharge, about 15% button opens voltage is less than 4.0V；As can be seen from Figure 2B, the type of the metal chloride of addition is more, and the ratio of the button cell of existing self discharge is got over Small, wherein the most obvious with embodiment 6, only the open-circuit voltage of 4% button cell is less than 4.0V；And comparative example 1~3 is as just There are more serious self discharge, the open-circuit voltages of about 20% button cell to be less than 4.0V for the button cell of pole material.
The preparation method of metal impurities in removal nickel-cobalt lithium manganate material provided by the present invention passes through addition and nickel cobalt The corresponding metal chloride of metal impurities in LiMn2O4 sintering feed, and in conjunction with ammonium hydroxide, there is specific aim and efficiently go Except metal impurities；Meanwhile by the preparation method, the magnetic impurities such as iron can not only be removed, moreover it is possible to remove copper removal, chromium, zinc etc. Non-magnetic impurity；And preparation method is simple, easy to operate, to prepare high safety performance, nickel with trace metal impurity Cobalt lithium manganate material electrode material, for realizing the production of power-type lithium ion battery electrode material, new-energy automobile being promoted to produce The problems such as industry develops, has important practical significance.
Embodiment of above is only used to illustrate the technical scheme of the present invention and not to limit it, although referring to the above preferable embodiment party Formula describes the invention in detail, those skilled in the art should understand that, it can be to technical solution of the present invention It modifies or equivalent replacement should not all be detached from the spirit and scope of technical solution of the present invention.

Claims (15)

1. a kind of preparation method of the nickel-cobalt lithium manganate material with trace metal impurity, which comprises the following steps:
Nickle cobalt lithium manganate sintering feed is provided, the nickle cobalt lithium manganate sintering feed includes metal impurities；
Metal chloride solutions are provided, ammonium hydroxide are added in Xiang Suoshu metal chloride solutions, so that the metal chloride solutions In metal chloride and the ammonium hydroxide occur complex reaction formed alkaline etch bath；And
The nickle cobalt lithium manganate sintering feed and the alkaline etch bath are mixed, so that the alkaline etch bath is to the nickel cobalt mangaic acid Metal impurities in lithium sintering feed are etched, and obtain the nickel-cobalt lithium manganate material with trace metal impurity.
2. the preparation method of the nickel-cobalt lithium manganate material according to claim 1 with trace metal impurity, feature exist In the chemical formula of the metal chloride is MCld, wherein M includes at least one of copper, iron, chromium and zinc, 2≤d≤3；Institute The concentration for stating metal chloride described in metal chloride solutions is 0.01mol/L~0.1mol/L.
3. the preparation method of the nickel-cobalt lithium manganate material according to claim 2 with trace metal impurity, feature exist In the alkaline etch bath includes M (NH3)2dCld, the M (NH3)2dCldMole be greater than or equal to the metal impurities Mole.
4. the preparation method of the nickel-cobalt lithium manganate material according to claim 1 with trace metal impurity, feature exist In the pH of the alkaline etch bath is 9~12.
5. the preparation method of the nickel-cobalt lithium manganate material according to claim 1 with trace metal impurity, feature exist In the metal impurities include transition metal, and the metal ion in the metal chloride belongs to same with the transition metal Kind element.
6. the preparation method of the nickel-cobalt lithium manganate material according to claim 5 with trace metal impurity, feature exist In the metal impurities include at least one of copper, iron, chromium and zinc.
7. the preparation method of the nickel-cobalt lithium manganate material according to claim 1 with trace metal impurity, feature exist In including nickle cobalt lithium manganate in the nickle cobalt lithium manganate sintering feed, the chemical formula of the nickle cobalt lithium manganate is LizNixCoyMn1-x- yO2, wherein 1≤z≤1.05,0≤x≤1,0≤y≤1,0≤x+y≤1.
8. the preparation method of the nickel-cobalt lithium manganate material according to claim 1 with trace metal impurity, feature exist In the nickle cobalt lithium manganate sintering feed after lithium salts and transition metal oxide sintering by obtaining；The lithium salts includes lithium carbonate Or at least one of lithium hydroxide, the chemical formula of the transition metal oxide meet NiaCobMn1-a-b(OH)2Or NiaCobMn1-a-bCO3At least one of, wherein 0≤a≤1,0≤b≤1,0≤a+b≤1.
9. the preparation method of the nickel-cobalt lithium manganate material according to claim 8 with trace metal impurity, feature exist In the temperature of the sintering is 850 DEG C~950 DEG C；The atmosphere of the sintering is that air atmosphere, oxygen atmosphere or air oxygen are mixed Gas is closed, the oxygen concentration in air oxygen gaseous mixture is between 20%~100%.
10. the preparation method of the nickel-cobalt lithium manganate material according to claim 1 with trace metal impurity, feature exist In further including washing step after etching reaction occurs, the washing step includes:
By the nickle cobalt lithium manganate sintering feed filtering after generation etching reaction, filter cake is obtained；And
The filter cake is washed, filtered, dried, is sieved, the nickle cobalt lithium manganate material with trace metal impurity is obtained Material.
11. a kind of nickel-cobalt lithium manganate material with trace metal impurity, which is characterized in that described with trace metal impurity Nickel-cobalt lithium manganate material of the nickel-cobalt lithium manganate material as described in claim 1-10 any one with trace metal impurity Obtained by preparation method.
12. the nickel-cobalt lithium manganate material according to claim 11 with trace metal impurity, which is characterized in that the trace The nickel-cobalt lithium manganate material for measuring metal impurities includes nickle cobalt lithium manganate and metal impurities, and the metal impurities are doped in the nickel cobalt In LiMn2O4, the metal impurities include copper, and the content of the copper is lower than 30ppb.
13. the nickel-cobalt lithium manganate material according to claim 12 with trace metal impurity, which is characterized in that the gold Belonging to impurity also includes zinc and chromium, and the content of the zinc is lower than 30ppb, and the content of the chromium is lower than 40ppb.
14. the nickel-cobalt lithium manganate material according to claim 12 with trace metal impurity, which is characterized in that the gold The total content for belonging to impurity is lower than 100ppb.
15. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes such as claim 11-14 any one institute The nickel-cobalt lithium manganate material with trace metal impurity stated.
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