CN106711450B - A kind of preparation method of the using lithium bicarbonate lithium battery anode proprietary material for lithium source - Google Patents
A kind of preparation method of the using lithium bicarbonate lithium battery anode proprietary material for lithium source Download PDFInfo
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- CN106711450B CN106711450B CN201710019798.8A CN201710019798A CN106711450B CN 106711450 B CN106711450 B CN 106711450B CN 201710019798 A CN201710019798 A CN 201710019798A CN 106711450 B CN106711450 B CN 106711450B
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- battery anode
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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
- H01M4/58—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of lithium battery anode proprietary material for lithium source that uses lithium bicarbonate, use high-purity lithium bicarbonate for lithium source, first by hydroxide M (OH) x of M metal (x=1,2,3 ...) it is added in high-purity lithia water by certain mol proportion, it is stirred, keeps certain vacuum degree, control mixing time and evaporating temperature, when solution becomes thick state, heat up atmospheric evaporation, after presoma is completely dried, carries out high-temperature roasting.The invention has the benefit that directlying adopt high-purity lithia water as lithium source, Active components distribution is uniform in the presoma of preparation gone out, and crystal property is good, and charging and discharging capacity is big.
Description
Technical field
The present invention relates to technical field of lithium batteries, mainly a kind of to use lithium bicarbonate dedicated for the lithium battery anode of lithium source
The preparation method of material.
Background technique
Lithium battery has many characteristics, such as that operating voltage is high, specific energy is big, memoryless benefit, pollution is small, has extended cycle life.Cause
This, lithium battery obtains common application in the various mobile electronic devices such as portable phone, laptop, video camera, with
The continuous development of technology, the high capacity lithium ion battery developed at present have been applied on electric car.
Lithium ion battery is formed by anode, cathode and by diaphragm that positive and negative anodes separate, electrolyte, and inside battery uses spiral shell
Winding structure is revolved, diaphragm is a kind of very fine and the very strong polyethylene film material of permeability, and cathode is by graphitized carbon material
With the current collector composition of copper foil composition.Anode is made of cobalt acid lithium, LiMn2O4, LiFePO 4 or ternary material and aluminium foil
Current collector.Inside battery is filled with organic electrolyte solution.In addition it is also equipped with safety valve and PTC element, to protect battery.
The mass ratio of the positive and negative pole material of lithium ion battery is 3~4:1, and the performance of positive electrode directly affects lithium ion
The performance of battery occupies 40% or more ratio in the totle drilling cost of lithium ion battery.
At present prepare anode material for lithium-ion batteries method mainly have the characteristics of solid phase method and liquid phase method, solid phase method be by
Lithium source and nickel source or manganese source etc. directly carry out solid phase physical mixed, then by grinding, smashing, sintering repeatedly, also need sometimes
Corresponding active component could be obtained by auxiliary processes such as granulation or tablettings, sintering process generally requires 12~24 hours,
The even longer time.Liquid phase method is that lithium source will be configured to solution, and nickel source then is added or manganese source is co-precipitated, and filter,
It is dry, obtain positive electrode material precursor.The lithium source generallyd use is lithium hydroxide or lithium carbonate, and lithium source cannot be effective in this method
It is compound with nickel compound containing or cobalt compound, lead to that the presoma lithium density of preparation is low, crystallization is poor, such material caused to be given birth to
The battery specific capacity of production is low, poor circulation.
Summary of the invention
The problem of present invention aim to address existing liquid phase methods, and provide and a kind of use lithium bicarbonate for lithium source
Lithium battery anode proprietary material preparation method, lithia water low-temperature evaporation under negative pressure, the lithium bicarbonate of precipitation can
To be uniformly coated on the surface of the hydroxide of M metal, concentration entrainment effect is effectively avoided, when high-temperature roasting, decomposes and generates
Lithium carbonate uniformly mixed with the hydroxide of M metal, Active components distribution is uniform in the presoma prepared, crystal property
Good, charging and discharging capacity is big.
The object of the present invention is achieved by the following technical solutions.It is this to use lithium bicarbonate for the lithium battery of lithium source
The preparation method of positive proprietary material, including the following steps: high-purity lithia water is added into evaporating kettle by a., opens
Stirring；B. hydroxide M (OH) x of a certain amount of M metal is added into evaporating kettle, is configured to suspension, controls Li:M moles
Than stirring 0.5~2h for 0.95~1.2:1；C. continue to stir, open vacuum pump and heater switch, control vacuum degree in kettle be-
0.01~-0.1Mpa, evaporating temperature are 55~85 DEG C；D. when solution becomes thick state, heat up constant pressure and dry, evaporating temperature
It is 85~105 DEG C, after presoma is completely dried, is ground and roasted to get lithium battery anode proprietary material.
Further, M is nickel, cobalt, manganese, iron, vanadium, titanium, one in aluminium in hydroxide M (OH) x of the M metal
Kind is several.
Further, the partial size of hydroxide M (OH) x of the M metal is 5~50 μm.
Further, roasting condition in the step d are as follows: 600~800 DEG C of maturing temperature, 4~8h of calcining time.
The invention has the benefit that directlying adopt high-purity lithia water as lithium source, the presoma of preparation gone out
Middle Active components distribution is uniform, and crystal property is good, and charging and discharging capacity is big.
Specific embodiment
Below in conjunction with embodiment, the present invention will be described in detail:
A kind of preparation method of lithium battery anode proprietary material for lithium source that uses lithium bicarbonate of the invention, the skill of use
Art scheme is as follows, and high-purity carbonic acid is added by certain mol proportion in hydroxide M (OH) x (x=1,2,3 ...) of M metal first
It in hydrogen lithium solution, is stirred, keeps certain vacuum degree, control mixing time and evaporating temperature, become thick to solution
When state, heat up atmospheric evaporation, after presoma is completely dried, carries out high-temperature roasting.Specifically comprise the following steps:
A. high-purity lithia water is added into evaporating kettle, opens stirring；
B. hydroxide M (OH) x of a certain amount of M metal is added into evaporating kettle, is configured to solution or suspension, controls
Li:M molar ratio is 0.95~1.2, and mixing time is 0.5~2h,
C. continue to stir, open vacuum pump and heater switch, controlling vacuum degree in kettle is -0.01~-0.1Mpa, evaporation temperature
Degree is 55~85 DEG C；
D. when solution becomes thick state, heat up atmospheric evaporation, and evaporating temperature is 85~105 DEG C, complete to presoma
After drying, is ground and roasted to get lithium battery anode proprietary material.
In the present invention, the lithium source is high-purity lithia water, and purity reaches 99.99% or more.
In the present invention, the M metal is one or more of nickel, cobalt, manganese, iron, vanadium, titanium, aluminium, wherein M metal
The partial size of hydroxide M (OH) x is 5~50 μm.
In the present invention, roasting condition in the step d are as follows: 600~800 DEG C of maturing temperature, 4~8h of calcining time.
The reaction equation of step d in the present invention are as follows: 2LiHCO3+ M (OH) x=Li2CO3·M(OH)x+H2O+CO2, wherein
The lithium bicarbonate of precipitation becomes lithium carbonate after decomposing, and is uniformly coated on the surface M (OH) x.Further after roasting, conversion is completed,
Reaction equation are as follows: Li2CO3·M(OH)x→LiMOy+H2O+CO2(y=1,2,3 ...).LiMOy is lithium battery anode material
The active component of material.
Embodiment 1
High-purity lithia water after 10kg removal of impurities is added into evaporating kettle, lithium bicarbonate concentration are 10%, and unlatching is stirred
Mix, after the nickel hydroxide of 1.50kg is added, wherein nickel hydroxide partial size be 15 μm, mixing time 1h, control kettle in vacuum degree be-
0.05Mpa, evaporating temperature is 60 DEG C, and when solution becomes thick state, atmospheric evaporation, evaporating temperature is 105 DEG C, to presoma
It after being completely dried, is ground and is roasted, 800 DEG C of maturing temperature, calcining time 6h is to get lithium battery anode proprietary material, warp
XRD analysis, active component are lithium nickelate crystal, wherein 0.1C first charge-discharge specific capacity is 145mAh/g, in 2C at -20 DEG C
Specific discharge capacity is 131mAh/g.
Embodiment 2
High-purity lithia water after 10kg removal of impurities is added into evaporating kettle, lithium bicarbonate concentration are 10%, and unlatching is stirred
Mix, after the cobalt hydroxide of 1.25kg is added, wherein cobalt hydroxide partial size be 20 μm, mixing time 1h, control kettle in vacuum degree be-
0.06Mpa, evaporating temperature is 50 DEG C, and when solution becomes thick state, atmospheric evaporation, evaporating temperature is 105 DEG C, to presoma
It after being completely dried, is ground and is roasted, 800 DEG C of maturing temperature, calcining time 6h is to get lithium battery anode proprietary material, warp
XRD analysis, active component are cobalt acid lithium crystal.Wherein at -20 DEG C, 0.1C first charge-discharge specific capacity is 146mAh/g, in 2C
Specific discharge capacity is 131mAh/g.
Embodiment 3
High-purity lithia water after 10kg removal of impurities is added into evaporating kettle, lithium bicarbonate concentration are 10%, and unlatching is stirred
Mix, be added 1.19kg manganous hydroxide after, wherein manganous hydroxide partial size be 20 μm, mixing time 1h, control kettle in vacuum degree be-
0.07Mpa, evaporating temperature is 40 DEG C, and when solution becomes thick state, atmospheric evaporation, evaporating temperature is 105 DEG C, to presoma
It after being completely dried, is ground and is roasted, 800 DEG C of maturing temperature, calcining time 6h is to get lithium battery anode proprietary material, warp
XRD analysis, active component are mangaic acid crystalline lithium.Wherein at -20 DEG C, 0.1C first charge-discharge specific capacity is 147mAh/g, in 2C
Specific discharge capacity is 132mAh/g.
Contrast sample is the positive electrode for using lithium carbonate as lithium source, and specific experiment scheme is, using lithium carbonate suspension
It is mixed with M (OH) x, other same the technical program of step measure result are as follows: at -20 DEG C, 0.1C first charge-discharge specific capacity is
96mAh/g is 85mAh/g in 2C specific discharge capacity.
It is understood that the above-mentioned specific embodiment technical solution that the invention is not limited in any way, all to adopt
It is all belonged to the scope of protection of the present invention with the mode of equivalent replacement or equivalent exchange technical solution obtained.
Claims (4)
1. a kind of preparation method for the lithium battery anode proprietary material for lithium source that uses lithium bicarbonate, which is characterized in that including with
Under several steps:
A. high-purity lithia water is added into evaporating kettle, opens stirring；
B. hydroxide M (OH) x of a certain amount of M metal is added into evaporating kettle, is configured to suspension, controls Li:M molar ratio
For 0.95~1.2:1,0.5~2h is stirred；
C. continue to stir, open vacuum pump and heater switch, controlling vacuum degree in evaporating kettle is -0.01~-0.1Mpa, evaporation temperature
Degree is 55~85 DEG C；
D. when solution becomes thick state, heat up constant pressure and dry, and evaporating temperature is 85~105 DEG C, is completely dried to presoma
Afterwards, it is ground and is roasted to get lithium battery anode proprietary material.
2. the preparation method of the lithium battery anode proprietary material for lithium source according to claim 1 that uses lithium bicarbonate,
Be characterized in that: M is one or more of nickel, cobalt, manganese, iron, vanadium, titanium, aluminium in hydroxide M (OH) x of the M metal.
3. the preparation method of the lithium battery anode proprietary material for lithium source according to claim 1 or 2 that uses lithium bicarbonate,
It is characterized by: the partial size of hydroxide M (OH) x of the M metal is 5~50 μm.
4. the preparation method of the lithium battery anode proprietary material for lithium source according to claim 1 that uses lithium bicarbonate,
It is characterized by: roasting condition in the step d are as follows: 600~800 DEG C of maturing temperature, 4~8h of calcining time.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089151A (en) * | 1999-09-13 | 2001-04-03 | Ishihara Sangyo Kaisha Ltd | Production of lithium manganate and lithium battery using the lithium manganate |
| CN102683671A (en) * | 2012-05-07 | 2012-09-19 | 宁德新能源科技有限公司 | Lamellar lithium-nickel composite oxide anode material |
| WO2016087716A1 (en) * | 2014-12-02 | 2016-06-09 | Keliber Oy | Method of producing lithium metal phosphates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089151A (en) * | 1999-09-13 | 2001-04-03 | Ishihara Sangyo Kaisha Ltd | Production of lithium manganate and lithium battery using the lithium manganate |
| CN102683671A (en) * | 2012-05-07 | 2012-09-19 | 宁德新能源科技有限公司 | Lamellar lithium-nickel composite oxide anode material |
| WO2016087716A1 (en) * | 2014-12-02 | 2016-06-09 | Keliber Oy | Method of producing lithium metal phosphates |
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Effective date of registration: 20191223 Address after: 314000 401, building 32, Hangzhou bay new economic Park, Jiaxing Port Area, Zhejiang Province Patentee after: Zhejiang Haiti New Material Technology Co., Ltd Address before: Yuhang District of Hangzhou City, Zhejiang Province, 311113 Liangzhu Street Bridge Village Qixian Haihong new materials science and Technology Park Patentee before: Zhejiang Haihong Holding Co.,Ltd. |