CN106856239A - High-pressure solid anode material for lithium-ion batteries and preparation method thereof - Google Patents

High-pressure solid anode material for lithium-ion batteries and preparation method thereof Download PDF

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Publication number
CN106856239A
CN106856239A CN201611208558.4A CN201611208558A CN106856239A CN 106856239 A CN106856239 A CN 106856239A CN 201611208558 A CN201611208558 A CN 201611208558A CN 106856239 A CN106856239 A CN 106856239A
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China
Prior art keywords
lithium
anode material
pressure solid
ion batteries
preparation
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CN201611208558.4A
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Chinese (zh)
Inventor
王�华
吴飞
高腾飞
顾家林
张川
李庆武
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Wulong Power (chongqing) Lithium Material Co Ltd
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Wulong Power (chongqing) Lithium Material Co Ltd
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Priority to CN201611208558.4A priority Critical patent/CN106856239A/en
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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
    • H01M4/48—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M4/52—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation method of high-pressure solid anode material for lithium-ion batteries, including step：(1) take D50 and be respectively 3~10 μm, 10~20 μm of nickel cobalt manganese hydroxide materials P1 and P2 mixing, the mass ratio of P1 and P2 is 10~35:65~90, P1 and P2 are same materials；(2) P1 the and P2 mixtures in step (1) are weighed, in molar ratio Li:(Ni+Co+Mn) it is 1~1.10:1 weighs lithium salts mixes with the mixture of P1 and P2, then the powder of mixing is placed in stove and is warming up to 600~1000 DEG C, and insulation obtains high-pressure solid nickel-cobalt-manganternary ternary anode material for 5~30 hours, and the lithium salts is LiOHH2O or Li2CO3.Also disclose the cell positive material prepared by preceding method.The method changes the size distribution of persursor material, the shortcoming low so as to improve single presoma compacted density.

Description

High-pressure solid anode material for lithium-ion batteries and preparation method thereof
Technical field
The invention belongs to lithium ion battery material technical field, and in particular to a kind of high-pressure solid anode material for lithium-ion batteries And preparation method thereof.
Background technology
In numerous battery products, lithium ion battery is due to light weight, small volume, operating voltage be high, energy is close Degree height, output power, self-discharge rate is low, charge efficiency is high, paid close attention to by people the advantages of have extended cycle life, in hand The fields such as machine, notebook computer are widely used.
In current commercialized anode material for lithium-ion batteries, cobalt acid lithium is used as earliest commercialized lithium ion cell positive Material has the advantages that high-pressure solid, high-energy-density.But due to the shortage of cobalt resource, price is also costly.Before most having at present Scape substitution cobalt acid lithium is exactly ternary nickel cobalt manganese cathode material, the continuous production that production nickel cobalt manganese hydroxide precursor is used Formula coprecipitation reaction kettle, and the ternary material precursor that co-precipitation is obtained is the spherical agglomerates reunited by primary particle, There is more hole, the distribution of particle diameter is also unable to reach the requirement of high compacted density, therefore cannot accomplish as cobalt acid lithium The same high-pressure solid.
The content of the invention
Regarding the issue above, the present invention provides a kind of step is simple, easily operated, prepare high-compaction-density lithium The method of ion battery positive electrode.
The present invention solves the technical scheme that its technical problem is used：A kind of preparation of high-pressure solid anode material for lithium-ion batteries Method, comprises the following steps：
(1) take D50 and be respectively 3~10 μm, 10~20 μm of nickel cobalt manganese hydroxide materials P1 and P2 mixing, P1's and P2 Mass ratio is 10~35:65~90, P1 and P2 are same nickel cobalt manganese hydroxide；
(2) P1 the and P2 mixtures in step (1) are weighed, in molar ratio Li:(Ni+Co+Mn) it is 1~1.10:1 weighs lithium Salt and the mixture of P1 and P2, mix, and then the powder of mixing is placed in stove and is warming up to 600~1000 DEG C, and insulation 5~30 is small When obtain high-pressure solid tertiary cathode material, the lithium salts is LiOHH2O or Li2CO3。
The nickel cobalt manganese hydroxide is NixMnyCoz(OH)2, wherein, 0 ＜ x≤1,0 ＜ y≤1,0 ＜ z≤1.
Preferably, the nickel cobalt manganese hydroxide is Ni0.5Mn0.3Co0.2(OH)2、Ni0.6Mn0.2Co0.2(OH)2、 Ni0.8Mn0.1Co0.1(OH)2Or Ni0.4Mn0.4Co0.2(OH)2In one kind.
The nickel cobalt manganese hydroxide is prepared using coprecipitation.
Preferably, the mass ratio of the P1 and P2 is 10~35:65~90.
Another object of the present invention is to provide a kind of high-pressure solid anode material for lithium-ion batteries, the material is by the above method Prepare.
The beneficial effects of the invention are as follows：By using two kinds of nickel cobalt manganese hydroxide precursors of difference D50, according to certain Ratio is mixed, and changes the size distribution of persursor material, the shortcoming not enough so as to improve single presoma compacting；After And by the way that with addition of Li salt, high temperature sintering synthesis of ternary positive electrode, the ternary material being distributed than single particle size has preferably compacting Density, so as to also have energy density higher using its battery for preparing.The method operating procedure is simple, technique is easily real Existing, raw material sources are wide, and market application value is high, is suitable for scale industrial production.
Brief description of the drawings
Fig. 1 is P1 in embodiment 1:P2 is respectively 0:100 and 20:The XRD spectrum of positive electrode obtained in 80.
Specific embodiment
With reference to embodiment, the invention will be further described, but not thereby limiting the invention.
Embodiment 1 prepares high-pressure solid anode material for lithium-ion batteries
First, high-pressure solid anode material for lithium-ion batteries is prepared
P1 and P2 is Ni in the present embodiment0.5Mn0.3Co0.2(OH)2, D50=5 μm of P1, D50=12 μm of P2, Li salt is adopted Use lithium carbonate.
Operate in accordance with the following steps：
(1) the D50=5 μm and D50=12 μm hydroxide Ni of particle diameter is prepared respectively using coprecipitation0.5Co0.2Mn0.3 (OH)2Persursor material P1 and P2, according to P1:P2=20:80 mass ratio is well mixed.
(2) by chemical composition analysis, Li in molar ratio:(Ni+Mn+Co) it is 1.04:1 ratio weighs Li respectively2CO3 With gained presoma P1 and P2 mixed-powder in step (1)；Then the powder of mixing is placed in atmosphere furnace, in air atmosphere Sintering, obtains LiNi0.5Mn0.3Co0.2O2Positive electrode；Calcination-temperature profile rises to 600 DEG C for room temperature, and heating rate is 5 DEG C/ Min, is then warming up to 1000 DEG C from 600 DEG C, and heating rate is 2 DEG C/min, is incubated 10 hours.Finally give high-pressure solid lithium ion Cell positive material LiNi0.5Mn0.3Co0.2O2。
2nd, contrast test：Prepare the LiNi of single particle size distribution0.5Mn0.3Co0.2O2
D50=12 μm of Ni is prepared using coprecipitation0.5Mn0.3Co0.2(OH)2Persursor material, in molar ratio Li:(Ni + Mn+Co) it is 1.04:1 ratio weighs Li respectively2CO3Uniformly mix with precursor powder；Then the powder that will mix is as gas In atmosphere stove, sinter in air atmosphere, obtain LiNi0.5Mn0.3Co0.2O2Positive electrode；Calcination-temperature profile rises to for room temperature 600 DEG C, heating rate is 5 DEG C/min, and 1000 DEG C are then warming up to from 600 DEG C, and heating rate is 2 DEG C/min, is incubated 10 hours. Finally give anode material for lithium-ion batteries LiNi0.5Mn0.3Co0.2O2。
3rd, different P1 are prepared:The high-pressure solid anode material for lithium-ion batteries of P2 ratios
Different P1 are prepared using the method for ", prepare high-pressure solid anode material for lithium-ion batteries ":The high pressure of P2 ratios Real anode material for lithium-ion batteries, material therefor is identical, Li:(Ni+Mn+Co) also it is 1.04:1, simply P1:The ratio of P2 is different (being specifically shown in Table 1), as a result table 1 below.
4th, experimental result
The anode material for lithium-ion batteries that preceding method is prepared carries out the detection of compacted density；By positive electrode and NMP and conductive agent are fabricated to pole piece after being prepared into slurry, and lithium piece does negative pole, are assembled into button cell and test its battery capacity. Result is as shown in table 1 below：
The difference of table 1 P1:The compacted density and capacity of the obtained product of P2 ratio materials
P1:P2 (mass ratio)
0:100 3.30 167.91
10:90 3.35 167.38
15:85 3.36 166.31
20:80 3.36 165.66
25:75 3.37 167.06
30:70 3.38 168.05
35:65 3.39 168.83
By P1:P2 is 20:Positive electrode obtained by 80 detected, obtains its XRD spectrum as shown in Figure 1, it is seen that will Raw material mixed, sinter after, raw material does not make material send structure change, is layer structure tertiary cathode material.
Embodiment 2 prepares high-pressure solid anode material for lithium-ion batteries
High-pressure solid is prepared according to the method in step in embodiment 1 ", prepare high-pressure solid anode material for lithium-ion batteries " Anode material for lithium-ion batteries, nickel cobalt manganese hydroxide selects Ni0.6Mn0.2Co0.2(OH)2Or Ni0.8Mn0.1Co0.1(OH)2Or Person Ni0.4Mn0.4Co0.2(OH)2, lithium salts uses LiOHH2O or Li2CO3, 5~30 hours are incubated under high temperature.Nickel cobalt manganese hydroxide Thing is prepared using coprecipitation method.Obtained positive electrode, NMP, conductive agent are mixed into pole piece, lithium are fabricated to after slurry Piece is assembled into button cell and tests its battery capacity as negative pole.The compacted density and battery of each material proportion and products obtained therefrom Capacity result is as shown in table 2.
The compacted density and capacity of the obtained product of the different materials of table 2

Claims (6)

1. a kind of preparation method of high-pressure solid anode material for lithium-ion batteries, it is characterised in that：Comprise the following steps：
(1) take D50 and be respectively 3~10 μm, 10~20 μm of nickel cobalt manganese hydroxide materials P1 and P2 mixing, the quality of P1 and P2 Than being 10~35:65~90, P1 and P2 are same nickel cobalt manganese hydroxide；
(2) P1 the and P2 mixtures in step (1) are weighed, in molar ratio Li:(Ni+Co+Mn) it is 1~1.10:1 weigh lithium salts with The mixture of P1 and P2, mixes, and then the powder of mixing is placed in stove and is warming up to 600~1000 DEG C, and insulation 5~30 hours is High-pressure solid nickel-cobalt-manganternary ternary anode material is obtained, the lithium salts is LiOHH2O or Li2CO3。
2. the preparation method of high-pressure solid anode material for lithium-ion batteries according to claim 1, it is characterised in that：The nickel Cobalt manganese hydroxide is NixMnyCoz(OH)2, wherein, 0 ＜ x≤1,0 ＜ y≤1,0 ＜ z≤1.
3. the preparation method of high-pressure solid anode material for lithium-ion batteries according to claim 2, it is characterised in that：The nickel Cobalt manganese hydroxide is Ni0.5Mn0.3Co0.2(OH)2、Ni0.6Mn0.2Co0.2(OH)2、Ni0.8Mn0.1Co0.1(OH)2Or Ni0.4Mn0.4Co0.2(OH)2In one kind.
4. the preparation method of high-pressure solid anode material for lithium-ion batteries according to claim 2, it is characterised in that：The nickel Cobalt manganese hydroxide is prepared using coprecipitation.
5. the preparation method of high-pressure solid anode material for lithium-ion batteries according to claim 1, it is characterised in that：The P1 It is 10~35 with the mass ratio of P2:65~90.
6. a kind of high-pressure solid anode material for lithium-ion batteries, it is characterised in that the method as described in any one of claim 1 to 5 Prepare.
CN201611208558.4A 2016-12-23 2016-12-23 High-pressure solid anode material for lithium-ion batteries and preparation method thereof Pending CN106856239A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807965A (en) * 2018-07-13 2018-11-13 金川集团股份有限公司 A kind of preparation method for high compacted density NCA positive electrodes
CN109524642A (en) * 2018-10-23 2019-03-26 桑顿新能源科技有限公司 A kind of mixing tertiary cathode material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102983326A (en) * 2012-09-20 2013-03-20 横店集团东磁股份有限公司 Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN105489881A (en) * 2016-01-12 2016-04-13 哈尔滨工业大学 Method for improving tap density of ternary nickel-cobalt-manganese cathode material for lithium-ion battery
CN105591094A (en) * 2016-01-05 2016-05-18 浙江瓦力新能源科技有限公司 Preparation method of high-performance spherical lithium manganate based cathode materials
CN105591096A (en) * 2016-03-03 2016-05-18 无锡凯力克能源材料有限公司 Industrial production method of nickel cobalt lithium manganite ternary positive electrode material with cycle life more than 3000 times

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102983326A (en) * 2012-09-20 2013-03-20 横店集团东磁股份有限公司 Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN105591094A (en) * 2016-01-05 2016-05-18 浙江瓦力新能源科技有限公司 Preparation method of high-performance spherical lithium manganate based cathode materials
CN105489881A (en) * 2016-01-12 2016-04-13 哈尔滨工业大学 Method for improving tap density of ternary nickel-cobalt-manganese cathode material for lithium-ion battery
CN105591096A (en) * 2016-03-03 2016-05-18 无锡凯力克能源材料有限公司 Industrial production method of nickel cobalt lithium manganite ternary positive electrode material with cycle life more than 3000 times

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807965A (en) * 2018-07-13 2018-11-13 金川集团股份有限公司 A kind of preparation method for high compacted density NCA positive electrodes
CN109524642A (en) * 2018-10-23 2019-03-26 桑顿新能源科技有限公司 A kind of mixing tertiary cathode material and preparation method thereof
CN109524642B (en) * 2018-10-23 2022-01-25 桑顿新能源科技有限公司 Mixed ternary cathode material and preparation method thereof

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