CN105375010A - Preparation method of high compaction density lithium ion cathode material - Google Patents

Preparation method of high compaction density lithium ion cathode material Download PDF

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CN105375010A
CN105375010A CN201510833930.XA CN201510833930A CN105375010A CN 105375010 A CN105375010 A CN 105375010A CN 201510833930 A CN201510833930 A CN 201510833930A CN 105375010 A CN105375010 A CN 105375010A
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preparation
lithium ion
mixed
compacted density
positive electrode
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CN105375010B (en
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郭忻
黄承焕
周耀
周友元
龚诚
李厦
胡柳泉
习小明
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Changsha Research Institute of Mining and Metallurgy Co Ltd
Hunan Changyuan Lico Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
Hunan Changyuan Lico 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
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/58—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
    • 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 relates to a preparation method of a high compaction density lithium ion cathode material. The preparation method comprises the following steps: (1) uniformly mixing a boron compound with a precursor material to obtain a pretreated precursor material; (2) sufficiently mixing the pretreated precursor material with a lithium salt to obtain a mixture; and (3) carrying out solid phase sintering on the mixture in an oxidizing atmosphere, cooling and crushing to obtain the high compaction density lithium ion cathode material. According to the preparation method, the precursor material is pretreated, the boron compound is firstly uniformly attached to the precursor, and then the pretreated precursor material is mixed with the lithium salt for sintering, so that doped element boron is uniformly distributed in a product phase so as to achieve the purpose of uniform doping. According to the high compaction density lithium ion cathode material prepared by the invention, the tap density is greater than or equal to 2.3 g/cm<3>, the manufacturing compaction density is greater than or equal to 3.70 g/cm<3>, the primary discharge gram capacity can reach more than 153 mAh/g, and the circulating capacity retention rate in 300 circles reaches more than 85%.

Description

A kind of preparation method of high compacted density lithium ion positive electrode
Technical field
The present invention relates to a kind of preparation method of cell positive material, particularly relate to a kind of preparation method of high compacted density lithium ion positive electrode.
Background technology
The advantages such as lithium rechargeable battery has that specific capacity is high, operating voltage is high, operating temperature range is wide, self-discharge rate is low, has extended cycle life, memory-less effect, pollution-free, lightweight, security performance is good, are widely used in electrical type consumer products, electric vehicle and energy storage field.
In recent years, along with mobile phone, notebook fast development, the digital product of various employing lithium ion battery upgrades updating speed very soon, and product is mostly tending towards portability, economization; Meanwhile, for preserving the ecological environment and ensureing the strategic demand of national energy security, electric automobile becomes new-energy automobile development priority, along with the growth requirement of electric automobile and hybrid vehicle, has higher requirement to the energy density of lithium ion battery; At present for the LiMn2O4 of electrokinetic cell and the energy density of LiFePO 4 on the low side, by progressively had the ternary electrokinetic cell of more high-energy-density replace.
But tertiary cathode material compacted density traditional is at present 3.3 ~ 3.4g/cm 3, compared with cobalt acid lithium, compacted density is on the low side, constrains the application of this material on the lithium ion battery of high-energy-density (particularly volumetric specific energy density requirements is high).Improving the compacted density of positive electrode, is a kind of energy density effective way improving battery.
By micron presoma is ground to form nanoscale in Chinese patent application prospectus CN101847722A, then obtain micron single crystal granular by high temperature sintering, improve the compacted density of material; But particle prepared by this method is easily reunited, and operate wayward.In Chinese patent application prospectus CN102509784A, by adding organic additive when grinding, suppressing particle agglomeration when pyroreaction, obtaining single crystal grain, to improve the compacted density of material.But the batch mixing process of this method is more complicated, and introducing organic additive both increased cost, had again certain potential safety hazard.In Chinese patent application prospectus CN102593442A, trace element is mixed in presoma and lithium salts batch mixing process, obtained the positive electrode of high-energy-density again by high temperature sintering, but adopt this doping method, not easily doped chemical is mixed equably body mutually in.Though and its material maximum compacted density can reach 3.85g/cm3, its 1C specific discharge capacity is only 140mAh/g.The boron doped lithium ion anode material Li [Li that utilized coprecipitation and sol-gal process to prepare in Chinese patent application prospectus CN103413931A amn bco cni db x] O 2prepare hydroxide precursor by coprecipitation, then by presoma with after lithium salts mixing presintering, mix a certain amount of boron compound, carry out second time sintering, obtain target product, this kind of method be presoma to mix with lithium salts carry out pre-burning after the boron compound that mixes, therefore need to carry out second time sintering, and, material after presintering has begun to take shape the crystal structure of target product, mixes boron compound on this basis, in boron element product lattice more difficult to get access.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, the method for the high compacted density lithium ion positive electrode providing a kind of energy consumption low, cost-saving, the compacted density>=3.70g/cm of the lithium ion anode material of preparation 3, 1C gram volume>=153mAh/g.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A preparation method for high compacted density lithium ion positive electrode, comprises the following steps:
(1) mixed with persursor material by boron compound, wherein said persursor material is Ni xco ym 1-x-y(OH) 2, Ni xco ym 1-x-ycO 3or Ni xco ym 1-x-yo 2, wherein 0.4≤x≤1,0≤y≤0.4, and 1-x-y>=0, M is one or more in Mn, Al, Ti, Mg; Persursor material adopts the preparation of prior art conventional method;
(2) mixture that step (1) obtains fully is mixed with lithium salts, obtain compound;
(3) compound that step (2) obtains is carried out solid-phase sintering in oxidizing atmosphere, cooling, fragmentation, namely obtain described high compacted density lithium ion positive electrode.
Above-mentioned preparation method, preferably, in described step (1), the mixed process of boron compound and persursor material is dry mixed or wet-mixed; Described dry mixed is mixed by mechanical ball milling with presoma by boron compound; Described wet-mixed be first boron compound is dissolved in solvent form clarification solution after, then add persursor material under agitation, continue stirring until and mix, finally dry.
Above-mentioned preparation method, preferably, in described dry mixing process, mechanical ball time consuming is 1 ~ 10h, and ball material mass ratio (hereinafter referred to as ratio of grinding media to material) is 1:1 ~ 10:1.
Above-mentioned preparation method, preferably, in described wet blending process, persursor material and solvent quality are than being 1:0.25 ~ 1:100; Described solvent be selected from water, ethanol, acetic acid one or more.
Above-mentioned preparation method, preferably, in described wet blending process, after adding persursor material, the time of Keep agitation is 10 ~ 1000min.
Above-mentioned preparation method, preferably, described boron compound be selected from boric acid, boron oxide one or both; The addition of boron compound accounts for the 0.1wt.% ~ 10wt.% of persursor material and boron compound gross mass.
Above-mentioned preparation method, preferably, in described step (2), lithium salts is selected from LiOH, Li 2cO 3, LiNO 3, Li 2c 2o 4in one or more.
Above-mentioned preparation method, preferably, the addition of described lithium salts in elemental lithium, the Ni in Li and persursor material xco ym 1-x-ythe mol ratio of (Li and presoma in metal) is 1:0.95 ~ 1:1.2.
Above-mentioned preparation method, preferably, in described step (3), oxidizing atmosphere is air or oxygen; Solid-phase sintering process is divided into double sintering: be first warming up to 500 ~ 700 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 3 ~ 10h; Be warming up to 701 ~ 1000 DEG C again, insulation 5 ~ 25h.Because the eutectic point of lithium salts and presoma is in this stage, adopt multi-steps sintering can ensure that presoma and lithium salts can fully react.
Above-mentioned preparation method, preferably, the general formula of the high compacted density lithium ion positive electrode of acquisition is LiNi aco bm cb 1-a-b-co 2, wherein 0.4≤a≤1,0≤b≤0.4,0≤c≤0.3, and 1-a-b-c > 0, M is one or more in Mn, Al, Ti, Mg; Compacted density>=the 3.70g/cm of described high compacted density lithium ion positive electrode 3.
Compared with prior art, the invention has the advantages that:
(1) preparation method of the present invention is by carrying out preliminary treatment to persursor material, by wet-mixed, boron compound is attached on presoma uniformly, sinter after more pretreated presoma being mixed with lithium salts, make doped chemical boron be uniformly distributed in product body mutually in, therefore can reach the object of Uniform Doped.
(2) boron compound first fully mixes with presoma by preparation method of the present invention, carries out mixed sintering again, just can make boron Uniform Doped by once sintered after mixing with lithium salts.
(3) the present invention is adulterated by boron element, promotes the growth of primary particle, forms the secondary spherical particles that crystal structure is stable, and the electro-chemical activity of reinforcing material; Meanwhile, by being optimized sintering process, strengthen the mechanical strength of product secondary agglomeration particle, and the final compacted density improving material.
(4) preparation process of the present invention only need adopt once sintered, is conducive to reducing energy consumption relative to the double sintering of prior art, cost-saving.
(5) its tap density>=2.3g/cm of high compacted density lithium ion positive electrode of preparing of the present invention 3, make compacted density>=3.70g/cm 3.The 1C gram volume that discharges first reaches more than 153mAh/g, and within 300 weeks, circulation conservation rate reaches more than 85%, has good processability, the advantages such as compacted density is high, stable cycle performance.
Accompanying drawing explanation
Fig. 1 is the electron-microscope scanning figure of high compacted density lithium ion battery positive electrode prepared by the embodiment of the present invention 1.
Fig. 2 is that high compacted density lithium ion battery positive electrode prepared by the embodiment of the present invention 1 makes the charging and discharging curve figure of battery.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, the various reagent used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
Embodiment 1:
A preparation method for high compacted density lithium ion battery positive electrode of the present invention, comprises the following steps:
(1) presoma preliminary treatment: by boric acid and absolute ethyl alcohol miscible, form the boric acid-ethanolic solution of transparent clarification, under stirring, add precursor powder Ni 0.5co 0.2mn 0.3(OH) 2, form suspension-turbid liquid, and Keep agitation 1 hour, then at 70 DEG C, carry out water-bath, and continue to be stirred to absolute ethyl alcohol evaporate to dryness, then carry out drying, obtain pretreated presoma.Wherein in suspension-turbid liquid, boric acid accounts for the 0.5wt.% of presoma and boric acid gross mass, and the mass ratio of presoma and ethanol is 1: 0.5.
(2) prepare burden: be placed in obtaining pretreated presoma in step (1) batch mixer with lithium carbonate and mix, control Li: (Ni 0.5co 0.2mn 0.3) mol ratio be 1.08, obtain compound.
(3) sinter: the compound obtained in step (2) is divided into double sintering in air atmosphere, is first first warming up to 650 DEG C by the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 950 DEG C again, insulation 10h, products therefrom sieved with stove cooling, fragmentation, namely obtains high compacted density lithium ion battery positive electrode LiNi 0.5co 0.2mn 0.295b 0.005o 2.
The electron-microscope scanning figure of high compacted density lithium ion battery positive electrode prepared by the present embodiment as shown in Figure 1, in figure, particle is the secondary spherical particle of being reunited by primary particle, its particle size is 3-5 μm, by the implementation method of the present embodiment, control growing up of monocrystal particle, compactness extent between particle is improved, enhances the mechanical strength of secondary agglomeration particle.
Obtained anode sizing agent after high compacted density lithium ion battery positive electrode, binding agent PVDF, solvent NMP and the conductive agent prepared with the present embodiment stir, anode sizing agent is evenly coated in the two-sided of aluminium foil, after drying, positive plate is carried out rolling making positive pole in pole piece roller compression machine, calculate making compacted density and the maximum compacted density of pole piece by measuring pole piece thickness, its tap density can reach 2.51g/cm 3, making compacted density can reach 3.72g/cm 3, maximum compacted density is 3.92g/cm 3.The negative material of certain producer is made cathode size be evenly coated on copper foil of affluxion body, drying, roll and make negative pole; Use 1.0moL/LLiPF 6/ EC+DMC (volume ratio 1:1) is as electrolyte, Celgard2300 is barrier film, be assembled into 523450 shell with square aluminum lithium ion batteries, test its chemical property, its charging and discharging curve as shown in Figure 2, within the scope of 2.8 ~ 4.2V, its 1C first discharge specific capacity is 155.3mAh/g, and energy density per unit volume metric density reaches 577.7mAh/cm 3, through circulation in 300 weeks, its circulation conservation rate reached 89.5%.
Comparative example 1:
The preparation method of the anode material for lithium-ion batteries of this comparative example, comprises the following steps:
(1) prepare burden: by precursor powder Ni 0.5co 0.2mn 0.3(OH) 2be placed in batch mixer with lithium carbonate to mix, control Li: (Ni 0.5co 0.2mn 0.3) mol ratio be 1.08, obtain compound.
(2) sinter: adopt embodiment 1 to adopt identical sintering schedule the compound obtained in step (1), in air atmosphere, carry out multi-steps sintering, be first warming up to 650 DEG C with the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 950 DEG C again, insulation 10h.Then products therefrom is sieved with fragmentation after stove cooling, namely obtain anode material for lithium-ion batteries LiNi 0.5co 0.2mn 0.3o 2.
After testing, the tap density of the anode material for lithium-ion batteries that this comparative example 1 is obtained is 2.2g/cm 3, make compacted density and reach 3.4g/cm 3, when this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram volume that discharges first is 158mAh/g, although comparatively embodiment 1 is high for its 1C gram volume, compacted density is lower, thus its energy density per unit volume metric density (537.2mAh/cm 3) lower than embodiment 1, through circulation in 300 weeks, its circulation conservation rate was 84.6%.
Embodiment 2:
A preparation method for high compacted density lithium ion battery positive electrode of the present invention, comprises the following steps:
(1) presoma preliminary treatment: by boric acid and absolute ethyl alcohol miscible, form the boric acid-ethanolic solution of transparent clarification, under stirring, add precursor powder Ni 0.5co 0.2mn 0.25mg 0.05cO 3, form suspension-turbid liquid, and Keep agitation 1 hour, be then placed in 70 DEG C of water-baths, continue to be stirred to solvent evaporate to dryness, drying, obtain pretreated presoma.Wherein in suspension-turbid liquid, boric acid accounts for the 0.5wt.% of presoma and boric acid gross mass, and the mass ratio of presoma and ethanol is 1: 0.5.
(2) prepare burden: obtain pretreated presoma in step (1) and be placed in batch mixer with lithium carbonate and mix, control Li: (Ni 0.5co 0.2mn 0.25mg 0.05) mol ratio be 1.08, obtain compound.
(3) sinter: the compound obtained in step (2) is carried out multi-steps sintering in air atmosphere, is first warming up to 650 DEG C by the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 950 DEG C again, insulation 10h, products therefrom sieved with stove cooling, fragmentation, namely obtains high compacted density lithium ion battery positive electrode LiNi 0.5co 0.2mn 0.25mg 0.045b 0.005o 2.
After testing, the high compacted density lithium ion battery positive electrode tap density that prepared by the present embodiment can reach 2.56g/cm 3, compacted density can reach 3.75g/cm 3.When this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram volume that discharges first is 155.9mAh/g, and its energy density per unit volume metric density reaches 584.6mAh/cm 3, through circulation in 300 weeks, its circulation conservation rate reached 88.9%.
Embodiment 3:
A preparation method for high compacted density lithium ion battery positive electrode of the present invention, comprises the following steps:
(1) presoma preliminary treatment: by boric acid and deionized water miscible, form the boric acid-aqueous solution of transparent clarification, in whipping process, add ternary precursor powder Ni 0.6co 0.2mn 0.2(OH) 2, form suspension-turbid liquid, and Keep agitation 1 hour, be then placed on electric furnace, continue to be stirred to moisture evaporate to dryness, then carry out drying, obtain pretreated ternary precursor material.Wherein in suspension-turbid liquid, the percentage that boric acid accounts for ternary precursor material and boric acid gross mass is 0.5wt.%, and the mass ratio of presoma and water is 1: 0.5.
(2) prepare burden: obtain pretreated ternary precursor in step (1) and be placed in batch mixer with lithium carbonate and mix, control Li: (Ni 0.6co 0.2mn 0.2) mol ratio be 1.10, obtain compound.
(3) sinter: the compound obtained in step (2) is carried out multistage sintering in air atmosphere, is first warming up to 650 DEG C with the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 900 DEG C again, insulation 10h, products therefrom sieved with fragmentation after stove cooling, namely obtains high compacted density lithium ion battery positive electrode LiNi 0.6co 0.2mn 0.195b 0.005o 2.
After testing, the high compacted density lithium ion battery positive electrode tap density that prepared by the present embodiment can reach 2.43g/cm 3, compacted density can reach 3.70g/cm 3, when this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram specific capacity of discharging first is 163.2mAh/g, and through circulation in 300 weeks, its circulation conservation rate reached 87.7%.
Embodiment 4:
A preparation method for high compacted density lithium ion battery positive electrode of the present invention, comprises the following steps:
(1) presoma preliminary treatment: boric acid is first ground, then carry out with 200 eye mesh screens process of sieving, then by the boric acid after process of sieving and ternary precursor material Ni 0.8co 0.1mn 0.1(OH) 2be placed in ball mill ball milling 2h, wherein ratio of grinding media to material is 1.2: 1, obtains pretreated ternary precursor material.
(2) prepare burden: the pretreated ternary precursor material obtained in step (1) is placed in batch mixer with lithium hydroxide and mixes, and control Li: (Ni 0.8co 0.1mn 0.1) mol ratio be 1.08, obtain compound.
(3) sinter: the compound obtained in step (2) is carried out multi-steps sintering in oxygen atmosphere, be first warming up to 550 DEG C with the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 780 DEG C again, insulation 10h, then products therefrom is sieved with stove cooling, fragmentation, namely obtain high compacted density lithium ion battery positive electrode LiNi 0.8co 0.1mn 0.095b 0.005o 2.
After testing, the high compacted density lithium ion battery positive electrode tap density that prepared by the present embodiment can reach 2.40g/cm 3, compacted density can reach 3.70g/cm 3, when this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram volume that discharges first is 174.6mAh/g, and through circulation in 300 weeks, its circulation conservation rate reached 85.7%.
Comparative example 2:
The preparation method of the anode material for lithium-ion batteries of this comparative example, comprises the following steps:
(1) by ternary precursor material Ni 0.8co 0.1mn 0.1(OH) 2be placed in batch mixer with lithium hydroxide to mix, and control Li: (Ni 0.8co 0.1mn 0.1) mol ratio be 1.04, obtain compound;
(2) compound of gained is placed in oxygen atmosphere after 550 DEG C of sintering 6h, be placed in ball mill ball milling 2h together with boric acid, wherein ratio of grinding media to material is 1.2: 1; Ball milling terminates to be placed at 780 DEG C of sintering 10h in oxygen atmosphere, then is sieved with stove cooling, fragmentation by products therefrom, namely obtains anode material for lithium-ion batteries LiNi 0.8co 0.1mn 0.095b 0.005o 2.
After testing, the anode material for lithium-ion batteries tap density that prepared by this comparative example can reach 2.33g/cm 3, compacted density can reach 3.68g/cm 3, when this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram volume that discharges first is 170.0mAh/g.Though its compacted density and embodiment 4 are more or less the same, its 1C discharge capacity comparatively embodiment 4 is low, and through circulation in 300 weeks, its circulation conservation rate was 84%.
Embodiment 5:
A preparation method for high compacted density lithium ion battery positive electrode of the present invention, comprises the following steps:
(1) presoma preliminary treatment: by boron oxide and ethanol miscible, form the boron oxide-ethanolic solution of transparent clarification, add ternary precursor powder Ni while stirring 0.5co 0.2mn 0.3(OH) 2, form suspension-turbid liquid, and Keep agitation 1 hour, be then placed in 70 DEG C of water-baths, continue to be stirred to solvent evaporate to dryness, drying, obtain pretreated presoma.Wherein in suspension-turbid liquid, boron oxide accounts for the 1.0wt.% of presoma and boron oxide gross mass, and the mass ratio of presoma and ethanol is 1: 1.
(2) prepare burden: be placed in obtaining pretreated presoma in step (1) batch mixer with lithium carbonate and mix, control Li: (Ni 0.5co 0.2mn 0.3) mol ratio be 1.06, obtain compound.
(3) sinter: the compound obtained in step (2) is carried out multi-steps sintering in air atmosphere, is first warming up to 650 DEG C by the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 970 DEG C again, insulation 10h, products therefrom sieved with stove cooling, fragmentation, namely obtains high compacted density lithium ion battery positive electrode LiNi 0.5co 0.2mn 0.29b 0.01o 2.
After testing, the high compacted density lithium ion battery positive electrode tap density that prepared by the present embodiment can reach 2.6g/cm 3, compacted density can reach 3.80g/cm 3.When this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram volume that discharges first is 154.3mAh/g, and its energy density per unit volume metric density reaches 586.3mAh/cm 3, through circulation in 300 weeks, its circulation conservation rate reached 88.9%.
Embodiment 6:
A preparation method for high compacted density lithium ion battery positive electrode of the present invention, comprises the following steps:
(1) presoma preliminary treatment: by boron oxide and ethanol miscible, form the boron oxide-ethanolic solution of transparent clarification, add ternary precursor powder Ni while stirring 0.7co 0.15mn 0.15(OH) 2, form suspension-turbid liquid, and Keep agitation 1 hour, be then placed in 70 DEG C of water-baths, continue to be stirred to solvent evaporate to dryness, drying, obtain pretreated presoma.Wherein in suspension-turbid liquid, boron oxide accounts for the 2.0wt.% of presoma and boron oxide gross mass, and the mass ratio of presoma and ethanol is 1: 1.5.
(2) prepare burden: be placed in obtaining pretreated presoma in step (1) batch mixer with lithium carbonate and mix, control Li: (Ni 0.5co 0.2mn 0.3) mol ratio be 1.04, obtain compound.
(3) sinter: the compound obtained in step (2) is carried out multi-steps sintering in air atmosphere, is first warming up to 550 DEG C by the programming rate of 3 DEG C/min, insulation 6h; Be warming up to 800 DEG C again, insulation 10h, products therefrom sieved with stove cooling, fragmentation, namely obtains high compacted density lithium ion battery positive electrode LiNi 0.7co 0.15mn 0.13b 0.02o 2.
After testing, the high compacted density lithium ion battery positive electrode tap density that prepared by the present embodiment can reach 2.54g/cm 3, compacted density can reach 3.70g/cm 3.When this positive electrode is made into battery, within the scope of 2.8 ~ 4.2V, its 1C gram volume that discharges first is 167.2mAh/g, and through circulation in 300 weeks, its circulation conservation rate reached 86.2%.

Claims (10)

1. a preparation method for high compacted density lithium ion positive electrode, comprises the following steps:
(1) mixed with persursor material by boron compound, obtain pretreated persursor material, wherein said persursor material is Ni xco ym 1-x-y(OH) 2, Ni xco ym 1-x-ycO 3or Ni xco ym 1-x-yo 2, wherein 0.4≤x≤1,0≤y≤0.4, and 1-x-y>=0, M is one or more in Mn, Al, Ti, Mg;
(2) the pretreated persursor material that step (1) obtains fully is mixed with lithium salts, obtain compound;
(3) compound that step (2) obtains is carried out solid-phase sintering in oxidizing atmosphere, cooling, fragmentation, namely obtain described high compacted density lithium ion positive electrode.
2. preparation method as claimed in claim 1, it is characterized in that, in described step (1), the mixed process of boron compound and persursor material is dry mixed or wet-mixed; Described dry mixed is mixed by mechanical ball milling with presoma by boron compound; Described wet-mixed is after first boron compound being dissolved in solvent, then adds persursor material under agitation, continues stirring until and mixes, finally dry.
3. preparation method as claimed in claim 2, is characterized in that, in described dry mixing process, mechanical ball time consuming is 1 ~ 10h, and ratio of grinding media to material is 1:1 ~ 10:1.
4. preparation method as claimed in claim 2, is characterized in that, in described wet blending process, persursor material and solvent quality are than being 1:0.25 ~ 1:100; Described solvent be selected from water, ethanol, acetic acid one or more.
5. preparation method as claimed in claim 2, it is characterized in that, in described wet blending process, after adding persursor material, the time of Keep agitation is 10 ~ 1000min.
6. the preparation method as described in any one of claim 2 ~ 5, is characterized in that, described boron compound be selected from boric acid, boron oxide one or both; The addition of boron compound accounts for the 0.1wt.% ~ 10wt.% of persursor material and boron compound gross mass.
7. the preparation method as described in any one of claim 2 ~ 5, is characterized in that, in described step (2), lithium salts is selected from LiOH, Li 2cO 3, LiNO 3, Li 2c 2o 4in one or more.
8. preparation method as claimed in claim 7, is characterized in that, the addition of described lithium salts in elemental lithium, the Ni in Li and persursor material xco ym 1-x-ymol ratio be 1:0.95 ~ 1:1.2.
9. the preparation method as described in any one of claim 2 ~ 5, is characterized in that, in described step (3), oxidizing atmosphere is air or oxygen; Solid-phase sintering process is divided into double sintering: be first warming up to 500 ~ 700 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 3 ~ 10h; Be warming up to 701 ~ 1000 DEG C again, insulation 5 ~ 25h.
10. the preparation method as described in any one of claim 2 ~ 5, is characterized in that, the general formula of the high compacted density lithium ion positive electrode of acquisition is LiNi aco bm cb 1-a-b-co 2, wherein 0.4≤a≤1,0≤b≤0.4,0≤c≤0.3, and 1-a-b-c > 0, M is one or more in Mn, Al, Ti, Mg; Compacted density>=the 3.70g/cm of described high compacted density lithium ion positive electrode 3.
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