CN109850959A - A kind of technique preparing anode multicomponent material presoma using ammonia - Google Patents
A kind of technique preparing anode multicomponent material presoma using ammonia Download PDFInfo
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- CN109850959A CN109850959A CN201910120832.XA CN201910120832A CN109850959A CN 109850959 A CN109850959 A CN 109850959A CN 201910120832 A CN201910120832 A CN 201910120832A CN 109850959 A CN109850959 A CN 109850959A
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- ammonia
- material presoma
- multicomponent material
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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 techniques for preparing anode multicomponent material presoma using ammonia, belong to the fabricating technology field of cell positive material presoma, multi-element metal salting liquid is added in reactor, it is passed through ammonia into reactor and is reacted with bubbling or spray pattern, obtain suspension, suspension is aged, filters, and obtains filter cake and filtrate；By the Washing of Filter Cake and drying, ion battery anode material precursor is obtained；Ammonium salt product is made by evaporative crystallization in the filtrate or ammonia is recycled by ammonia still process, is recycled；The present invention can reduce reagent type used in technique, shorten process, reduce the complexity of technological operation, reduce the chemical substance in technique waste water, improve product quality.
Description
Technical field
The invention belongs to the fabricating technology fields of cell positive material presoma, and in particular to a kind of to utilize ammonia system
The technique of standby anode multicomponent material presoma.
Background technique
In the 21st century, energy crisis and environmental improvement are the significant challenges that country faces, therefore develop new energy
It is inexorable trend.Electrochmical power source has the good characteristics such as high energy conversion rate, high energy density, lesser environmental pollution,
Ion battery therein has high-energy density, high open circuit voltage, lesser self-discharge rate, memory-less effect, environmentally friendly
The advantages that, have become the first choice of secondary power supply, has in consumer battery product, new-energy automobile and energy-storage system field wide
Wealthy application market.
The positive electrode of ion battery is the significant components for constituting battery, by taking the positive electrode of lithium ion battery as an example, it
It is the multicomponent material being prepared by presoma and lithium-containing compound by certain physico-chemical process, presoma one therein
As be multi-element metal compound, mainly by the mixed solution containing metal salts such as nickel, cobalt, manganese and ammonium aqueous slkali co-precipitation generation,
The preparation method is as follows: first by the group certain density mixing salt solution containing metal ions such as nickel, cobalt, manganese of assignment system, then match
Certain density ammonia alkali mixed solution is made as precipitating reagent and complexing agent, continuously being passed through nitrogen makes reaction kettle atmosphere nitrogen
Cocurrent reaction is carried out after atmosphere, by adjusting the pH value of reaction solution, is generated complex precipitate, is filtered, washed, is dried in vacuo
After directly obtain presoma.In the preparation process of above-mentioned lithium ion cell positive multicomponent material presoma, ammonia alkali solution is heavy
Shallow lake agent and complexing agent, are formulated by caustic soda and ammonium hydroxide, and alkali therein is precipitating reagent, and ammonia is complexing agent；Due to being made using caustic soda
For precipitating reagent, not easy to wash and filtering is precipitated.Whole preparation process must carry out in a nitrogen atmosphere, to prevent product from aoxidizing.
The feed way of solution is affected to product quality in technique, and ammonia alkali and unreacted metal ion are contained in technique waste water.
From the preparation process of above-mentioned anode multicomponent material presoma can be seen that in whole process agents useful for same compared with
More, process flow is longer, complicated for operation, containing there are many chemical substances in technique waste water.Therefore, it is polynary to develop new anode
The preparation process of material precursor reduces reagent type used in technique, shortens process, reduces the complicated journey of technological operation
Degree, the chemical substance reduced in technique waste water are imperative.
Summary of the invention
The present invention provides a kind of techniques that anode multicomponent material presoma is prepared using ammonia, solve above-mentioned ask
Topic, the present invention are achieved by the following technical solution.
It is an object of the present invention to provide a kind of technique for preparing anode multicomponent material presoma using ammonia, including it is following
Step:
Multi-element metal salting liquid is added in reactor, ammonia is passed through into reactor with bubbling or spray pattern and is carried out
Reaction, obtains suspension；The suspension is aged, filters, and obtains filter cake and filtrate；By the Washing of Filter Cake and drying, obtain from
Sub- anode multicomponent material presoma；Ammonium salt product is made by evaporative crystallization in the filtrate or ammonia is recycled by ammonia still process
Gas is recycled.
Preferably, the multi-element metal concentration of salt solution is 1~2.5mol/L.
Preferably, it is 9.5~11.5 that the reaction condition, which is control pH, reacts 1h under room temperature.
Preferably, the multi-element metal salting liquid is transition metal soluble salt solutions.
Preferably, the multi-element metal salting liquid is nickel, the nitrate of cobalt or manganese Metal ion, sulfate or chloride salt
The mixing of one or more of solution.
Preferably, the washing process is to be washed with deionized filter cake 3 times.
Preferably, the reactor is gas-liquid two-phase reactor or gas-liquid-solid phase reaction device.
Preferably, the ion battery is lithium ion battery, sodium-ion battery or Magnesium ion battery.
Compared with prior art, the present invention has the following advantages:
(1) present invention process need not reuse caustic soda and nitrogen, to reduce the kind of chemical substance used in technique
Class；
(2) using ammonia as precipitating reagent, solid product is easy to wash and filter；
(3) caustic soda arrangement step is no longer needed in technique, thus shortens process flow；
(4) due to using gas precipitation agent, no longer it is two kinds of solution cocurrent adding materials, reduces the complicated journey of technological operation
Degree；
(5) due to not using caustic soda in technique, no longer occurs sodium ion in technique waste water, in waste water treatment process no longer
Have it is cheap, be difficult to the sodium salt product sold；
(6) product sale can be made up in the ammonium salt in technique of evaporative crystallization, and recycling ammonia can also be reacted by ammonia still process
Gas is recycled in process；
(7) present invention process can control the partial size of ion battery anode material precursor product produced well
Distribution, product cut size is small, and narrowly distributing, good product quality.
Detailed description of the invention
Fig. 1 is the process flow chart that the present invention prepares anode multicomponent material presoma using ammonia, and wherein ammonium salt is made
For byproduct recycling；
Fig. 2 is that the present invention using ammonia prepares the process flow chart of anode multicomponent material presoma, wherein ammonium salt into
Row ammonia still process, ammonia recycle use；
Fig. 3 is the grain size distribution of the presoma of anode multicomponent material prepared by embodiment 1.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific
The invention will be further described for embodiment and attached drawing, but illustrated embodiment is not as a limitation of the invention.
Experimental method and detection method described in following each embodiments are unless otherwise specified conventional method；The examination
Agent and material can be commercially available on the market unless otherwise specified.
As depicted in figs. 1 and 2: multi-element metal salt is made into mixed solution first by the present invention, is added to bubbling style reactor
In, when being sufficiently stirred, directly blast ammonia into reactor in a manner of being bubbled or spray, control solution pH value,
Reaction temperature, reaction time and digestion time, wherein the pH value of solution is controlled by control ammonia flow velocity and flow,
Then it is filtered, washed and is dried to obtain the presoma of anode multicomponent material；Filtrate can obtain ammonium salt by evaporative crystallization
Product can also recycle ammonia by ammonia still process, be recycled.
Embodiment 1
Nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved with deionized water, are configured to total metal ion in molar ratio for 8:1:1
Concentration is the multi-element metal salting liquid of 1.0mol/L, takes multi-element metal salting liquid 500mL that the bubble type that volume is 2000mL is added
In reactor, solution in stirred reactor, and controlled at 25 DEG C, the form that ammonia is bubbled is passed directly into reaction solution
Middle carry out precipitation reaction, ammonia flow 0.20g/min, isothermal reaction 1h, reacting liquid pH value 10.5 obtains suspension, old
Change 2h, vacuum filtration obtains filter cake and filtrate, is washed with deionized filter cake 3 times, dry cake obtains the polynary material of anode
The presoma of material；Filtrate obtains ammonium salt product by evaporative crystallization.
Embodiment 2
Nickel nitrate, cobalt nitrate, manganese nitrate are dissolved with deionized water, are configured to total metal ion in molar ratio for 1:1:1
Concentration is the multi-element metal salting liquid of 1.5mol/L, takes multi-element metal salting liquid 500mL that the bubble type that volume is 2000mL is added
In reactor, solution in stirred reactor, and controlled at 25 DEG C, the form that ammonia is bubbled is passed directly into reaction solution
Middle carry out precipitation reaction, ammonia flow 0.30g/min, isothermal reaction 1h, reacting liquid pH value 9.5 obtain suspension, ageing
2h, vacuum filtration, obtains filter cake and filtrate, is washed with deionized filter cake 3 times, dry cake obtains anode multicomponent material
Presoma；Filtrate obtains ammonium salt product by evaporative crystallization.
Embodiment 3
Nickel chloride, cobalt chloride, manganese chloride are dissolved with deionized water, are configured to total metal ion in molar ratio for 4:2:4
Concentration is the multi-element metal salting liquid of 2.0mol/L, takes multi-element metal salting liquid 500mL that the bubble type that volume is 2000mL is added
In reactor, solution in stirred reactor, and controlled at 25 DEG C, the form that ammonia is sprayed is passed directly into reaction solution
Middle carry out precipitation reaction, ammonia flow 0.40g/min, isothermal reaction 1h, reacting liquid pH value 10 obtain suspension, ageing
2h.Vacuum filtration, obtains filter cake and filtrate, is washed with deionized filter cake 3 times, dry cake obtains anode multicomponent material
Presoma, filtrate can steam ammonia by reacting with alkali, be recycled.
Embodiment 4
Nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved with deionized water, are configured to total metal ion in molar ratio for 8:1:1
Concentration is the multi-element metal salting liquid of 2.5mol/L, takes multi-element metal salting liquid 500mL that the bubble type that volume is 2000mL is added
In reactor, solution in stirred reactor, and controlled at 25 DEG C, the form that ammonia is sprayed is passed directly into reaction solution
Middle carry out precipitation reaction, ammonia flow 0.50g/min, isothermal reaction 1h, reacting liquid pH value 11.5 obtains suspension, old
Change 2h.Vacuum filtration, obtains filter cake and filtrate, is washed with deionized filter cake 3 times, dry cake obtains the polynary material of anode
The presoma of material, filtrate can steam ammonia by reacting with alkali, be recycled.
By taking embodiment 1 as an example, the particle diameter distribution situation of the presoma of anode multicomponent material prepared by the present invention is detected.
Using water as dispersing agent, product cut size is detected using laser fineness gage, as a result as shown in figure 3, can obtain in embodiment 1
The presoma D of the anode multicomponent material of preparation50It is 4.43 μm, D50Refer to that ratio shared by the particle less than the partial size is
50%, product cut size is small, and narrowly distributing, good product quality.It can thus be concluded that go out, by the present invention in that use ammonia as precipitating reagent,
Reaction is participated in instead of caustic soda and nitrogen, to reduce the type of chemical substance used in technique, shortens process flow,
The complexity of technological operation is reduced, while the ion battery anode material precursor product cut size prepared is small, and
Narrowly distributing, good product quality；In addition, due to not using caustic soda in technique, no longer occurs sodium ion in technique waste water, at waste water
There is no sodium salt products that is cheap, being difficult to sell in science and engineering skill；Production can be made up in ammonium salt in technique of evaporative crystallization
Product are sold, and recycling ammonia can also be reacted by ammonia still process, is recycled in process, is conducive to increase economic efficiency.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within be also intended to include these modifications and variations.
Claims (8)
1. a kind of technique for preparing anode multicomponent material presoma using ammonia, which comprises the following steps:
Multi-element metal salting liquid is added in reactor, ammonia is passed through into reactor with bubbling or spray pattern and is carried out instead
It answers, obtains suspension；The suspension is aged, filters, and obtains filter cake and filtrate；By the Washing of Filter Cake and drying, ion is obtained
Anode multicomponent material presoma；Ammonium salt product is made by evaporative crystallization in the filtrate or ammonia is recycled by ammonia still process,
It is recycled.
2. the technique according to claim 1 for preparing anode multicomponent material presoma using ammonia, which is characterized in that
The multi-element metal concentration of salt solution is 1~2.5mol/L.
3. the technique according to claim 1 for preparing anode multicomponent material presoma using ammonia, which is characterized in that
The reaction condition is that control pH is 9.5~11.5, reacts 1h under room temperature.
4. the technique according to claim 1 for preparing anode multicomponent material presoma using ammonia, which is characterized in that
The multi-element metal salting liquid is transition metal soluble salt solutions.
5. the technique according to claim 4 for preparing anode multicomponent material presoma using ammonia, which is characterized in that
The multi-element metal salting liquid be one of nickel, the nitrate of cobalt or manganese Metal ion, sulfate or chloride brine or
Several mixing.
6. the technique according to claim 1 for preparing anode multicomponent material presoma using ammonia, which is characterized in that
The washing process is to be washed with deionized filter cake 3 times.
7. the technique according to claim 1 for preparing anode multicomponent material presoma using ammonia, which is characterized in that
The reactor is gas-liquid two-phase reactor or gas-liquid-solid phase reaction device.
8. the technique that ammonia according to claim 1 prepares anode multicomponent material presoma, which is characterized in that described
Ion battery is lithium ion battery, sodium-ion battery or Magnesium ion battery.
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Citations (6)
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| CN102249348A (en) * | 2011-05-26 | 2011-11-23 | 中国科学院青海盐湖研究所 | Method for preparing hexagonal plate cobaltosic oxide |
| CN102800857A (en) * | 2012-09-11 | 2012-11-28 | 贵州红星发展股份有限公司 | Method for preparing ternary positive material precursor |
| CN106299340A (en) * | 2016-10-11 | 2017-01-04 | 苏州大学 | A kind of preparation method of modified tertiary cathode material |
| CN106558688A (en) * | 2016-11-18 | 2017-04-05 | 贵州振华新材料有限公司 | High-voltage lithium-battery cathode material, battery and preparation method and application |
| CN107768627A (en) * | 2017-10-03 | 2018-03-06 | 长沙仲善新能源科技有限公司 | A kind of high-temperature stability nickle cobalt lithium manganate combination electrode and preparation method and application |
| US10128494B2 (en) * | 2014-08-01 | 2018-11-13 | Apple Inc. | High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries |
-
2019
- 2019-02-18 CN CN201910120832.XA patent/CN109850959A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249348A (en) * | 2011-05-26 | 2011-11-23 | 中国科学院青海盐湖研究所 | Method for preparing hexagonal plate cobaltosic oxide |
| CN102800857A (en) * | 2012-09-11 | 2012-11-28 | 贵州红星发展股份有限公司 | Method for preparing ternary positive material precursor |
| US10128494B2 (en) * | 2014-08-01 | 2018-11-13 | Apple Inc. | High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries |
| CN106299340A (en) * | 2016-10-11 | 2017-01-04 | 苏州大学 | A kind of preparation method of modified tertiary cathode material |
| CN106558688A (en) * | 2016-11-18 | 2017-04-05 | 贵州振华新材料有限公司 | High-voltage lithium-battery cathode material, battery and preparation method and application |
| CN107768627A (en) * | 2017-10-03 | 2018-03-06 | 长沙仲善新能源科技有限公司 | A kind of high-temperature stability nickle cobalt lithium manganate combination electrode and preparation method and application |
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Application publication date: 20190607 |