CN109019702A - A kind of preparation method of porous nickel acid lithium anode material - Google Patents
A kind of preparation method of porous nickel acid lithium anode material Download PDFInfo
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- CN109019702A CN109019702A CN201810830978.9A CN201810830978A CN109019702A CN 109019702 A CN109019702 A CN 109019702A CN 201810830978 A CN201810830978 A CN 201810830978A CN 109019702 A CN109019702 A CN 109019702A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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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
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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
- H01M4/52—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
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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
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Abstract
The invention discloses a kind of preparation methods of porous nickel acid lithium anode material, include: that the organic formwork agent containing alkali is added in nickel salt ethanol solution, the color of heating stirring to reactant light green color is become from bottle green after room temperature it is closed stand be made nickel hydroxide colloidal sol；Gained colloidal sol is subjected to dynamic rotary aging and forms nickel hydroxide gel, then nickel hydroxide powder is made in drying；Nickel hydroxide powder and lithium hydroxide powder are mixed and deionized water is added after grinding uniformly and further walks grinding, blackish green blocks of solid obtained, which is carried out low-temperature plasma processing removed template method, after dry can be prepared by porous nickel acid lithium anode material.Lithium nickelate positive electrode prepared by the present invention has porous structure, provides more channels for the deintercalation of lithium ion, improves the specific discharge capacity, discharge-rate and cyclical stability of material prepared.Preparation method of the invention also have many advantages, such as simple process, mild condition, it is reproducible and be conducive to industrialization promotion.
Description
Technical field
The invention belongs to electrochemical technology fields, more particularly, to a kind of preparation method of porous nickel acid lithium anode material.
Background technique
Fast development due to global information industry in recent years and portable electronic product are (such as: laptop, digital phase
Machine and DV etc.) rapid proliferation, the requirement to battery performance is also higher and higher, particularly, excellent battery
Do not need only to have high capacity, high power, light weight, it is small in size and pollution-free the advantages that, safety and charge and discharge cycles
Service life must also be high, this greatly have stimulated the fast development and technological progress of battery industry.
Lithium ion battery electrode material is since high with operating voltage, specific energy is big, have extended cycle life, self discharge coefficient is small
And the advantages that memory-less effect, since the advent of the world is just by the concern of researcher.Lithium battery is mainly by positive electrode, cathode material
The composition such as material, electrolyte, diaphragm and conductive material, wherein the selection of positive and negative electrode material and quality directly determine the property of lithium battery
Energy and price.Therefore, the research of cheap, high performance positive and negative electrode material is always the emphasis of lithium battery industry development.Cathode material
Expect current development comparative maturity；And the research and development of positive electrode have become and restrict lithium battery performance and further increase and price
An important factor for further decreasing.Currently used anode material of lithium battery includes cobalt acid lithium, lithium nickelate, LiMn2O4 and ferric phosphate
Lithium, wherein cobalt acid lithium becomes earliest due to having many advantages, such as that heavy-current discharge, discharge voltage are high and steady and have extended cycle life
The anode material for lithium-ion batteries of commercialization, and it is widely used in small portable electronic device.However, the natural resources of cobalt
Limited and expensive, along with capacity is relatively low (reversible capacity is 110~150mAh/g), which greatly limits with cobalt acid
Lithium is the application of lithium ion battery and further increasing for performance of positive electrode.Lithium nickelate is to be expected to most having for substitution cobalt acid lithium
One of positive electrode of prospect, theoretical capacity 294mAh/g, actual capacity is up to 190~210mAh/g, and its is right
Environment influence is smaller, while having more advantage than cobalt acid lithium in price and resource, and lithium nickelate is as lithium ion cell positive at present
Material mainly faces the problem that capacity attenuation is serious under preparation method difficulty and high temperature.Therefore, a kind of easy nickel of operation is developed
The sour lithium preparation method and method of electric property that can improve prepared lithium nickelate positive electrode is necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of porous nickel acid lithium anode material.
In order to achieve the above objectives, solution of the invention is:
A kind of preparation method of porous nickel acid lithium anode material, specifically comprises the following steps:
(1) nickel salt is added to obtained solution A in dehydrated alcohol；
(2) aqueous slkali is added in template and stirs evenly obtained solution B；
(3) with vigorous stirring, solution B is slowly added dropwise into solution A, gained mixture is heated to 60 DEG C, and continues
Stirring 6h becomes light green color to the color of reaction-ure mixture from bottle green, stops stirring, by the closed standing of products therefrom room temperature
5h can be prepared by nickel hydroxide colloidal sol；
(4) by nickel hydroxide colloidal sol dynamic rotary aging 5h shape in 80 DEG C of homogeneous reactor obtained in step (3)
At nickel hydroxide gel, nickel hydroxide powder then is made after dry 12h in 110 DEG C of vacuum oven；
(5) nickel hydroxide powder and lithium hydroxide powder obtained in step (4) is mixed and is ground uniformly, is then added
Deionized water, further grinding is until gained mixture becomes blackish green dope；By the blackish green dope of gained at 110 DEG C
Blackish green blocks of solid is made in drying for 24 hours in vacuum oven；
(6) blackish green blocks of solid obtained in step (5) is made after powder and is put into dielectric barrier discharge (DBD) device
Middle progress low-temperature plasma handles removed template method, in oxygen atmosphere, 200 DEG C of temperature, voltage 350V and under the conditions of electric current 3.0A
4h is handled, then cooled to room temperature can be prepared by the porous nickel acid lithium material.
Preferably, the molar ratio of the nickel salt, alkali, template and lithium hydroxide is 1:5:30:1.
Preferably, the nickel salt is one of anhydrous acetic acid nickel, Dehydrated nickel chloride or anhydrous nitric acid nickel.
Preferably, the aqueous slkali is concentrated ammonia liquor.
Preferably, the template is one of dimethylformamide, dimethyl acetamide, pyridine or piperidines.
Relative to the existing method for preparing lithium nickelate positive electrode, the principle of the present invention and gain effect are as follows:
1. the present invention prepares the lithium nickelate positive electrode with porous structure by sol-gel method combination template,
Then by corona treatment, under lower temperature (200 DEG C), using in plasma ion, electronics, free radical with
And metastable particle etc., the template in lithium nickelate positive electrode is quickly and efficiently removed under the thermal decomposition temperature lower than lithium nickelate
Agent, so as to be effectively prevented from through (such as the particle growth of variety of problems existing for traditional high temperature sintering removed template method
Reunion and porous structure collapsing etc.), while the specific discharge capacity, discharge-rate and stable circulation of material prepared also can be improved
Property.
2. lithium nickelate positive electrode prepared by the present invention has porous structure, channel is provided for the deintercalation of lithium ion,
Ensure that with higher times of material prepared it is forthright.
3. the present invention provides a kind of new method for the preparation of lithium nickelate positive electrode, new approaches have been opened up.
4. preparation method of the invention also have simple process, mild condition, it is reproducible and be conducive to industrialization promotion
The advantages that.
Specific embodiment
Further below in conjunction with the embodiments with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, specific quality, reaction time in example
With the example that temperature, technological parameter etc. are also only in OK range, those skilled in the art is according to the present invention above-mentioned
Some nonessential modifications and adaptations that content is made all belong to the scope of protection of the present invention.
Embodiment 1:
Agents useful for same is not further purified as being commercial reagents without particularly pointing out using preceding.
The preparation method of porous nickel acid lithium anode material, specifically comprises the following steps:
(1) nickel acetate tetrahydrate is put into 110 DEG C of baking oven and is dried to constant weight, anhydrous acetic acid nickel is made；Weigh 1.77g
Anhydrous acetic acid nickel is added to the solution A for being made that molar concentration is 0.5M in dehydrated alcohol；
(2) concentrated ammonia liquor that 0.5mL mass percent concentration is 28% is added in 25mL dimethylformamide and is stirred
Even obtained solution B；
(3) with vigorous stirring, solution A is slowly added dropwise into solution B, gained mixture is heated to 60 DEG C, and continues
The color of stirring 6h to reaction-ure mixture becomes light green color from bottle green；Stop stirring, by the closed standing of products therefrom room temperature
5h can be prepared by nickel hydroxide colloidal sol；
(4) by nickel hydroxide colloidal sol, dynamic rotary aging 5h forms nickel hydroxide gel in 80 DEG C of homogeneous reactor,
Then nickel hydroxide powder is made after dry 12h in 110 DEG C of vacuum oven；
(5) nickel hydroxide powder and lithium hydroxide massage that are mixed than 1:1 and is ground uniformly, is then added
0.5ml deionized water, then be fully ground until mixture becomes blackish green dope；By the blackish green dope of gained at 110 DEG C
Vacuum oven in drying obtain blackish green blocks of solid for 24 hours；
(6) it is moved into dielectric barrier discharge (DBD) device after powder being made in blackish green blocks of solid, in oxygen atmosphere,
4h is handled under the conditions of 200 DEG C of temperature, voltage 350V and electric current 3.0A, then natural cooling can be prepared by target product porous nickel acid
Lithium material is denoted as LiNiO2-1。
Electric performance test condition: by 0.1g LiNiO2- 1,0.025g carbon black and 0.05g ptfe emulsion are in mortar
In be fully ground on uniform back loading to aluminium foil, can be prepared by afterwards containing LiNiO for 24 hours in 110 DEG C of vacuum drying2- 1 anode
Piece carries out the test of 1C high rate capability finally by charge and discharge instrument, and test result is shown in Table 1.
Embodiment 2:
The preparation of lithium nickelate material is referring to embodiment 1, the difference is that by the template dimethyl formyl in step (2)
Amine changes pyridine into.Remaining condition is identical, and porous nickel acid lithium material is made, is denoted as LiNiO2-2.Electric performance test with embodiment 1,
Test result is shown in Table 1.
Comparative example 1:
The preparation of lithium nickelate material is referring to embodiment 1, the difference is that by the template dimethyl formyl in step (2)
Amine changes the ethanol solution of polyethylene glycol PEG6000 into.Remaining condition is identical, and porous nickel acid lithium material is made, is denoted as LiNiO2-3。
For electric performance test with embodiment 1, test result is shown in Table 1.
Comparative example 2
The preparation of lithium nickelate material is referring to embodiment 1, the difference is that the method for Template removal becomes in step (6)
It is sintered 12 hours obtained porous nickel acid lithium materials at 950 DEG C, is denoted as LiNiO2- 4. electric performance tests are the same as embodiment 1, test result
It is shown in Table 1.
1 porous nickel acid lithium anode material electrical performance data of table
| Positive electrode | Gram volume (mAh/g) | 1C/2000 times (%) | |
| Embodiment 1 | LiNiO2-1 | 141 | 92.16 |
| Embodiment 2 | LiNiO2-2 | 139 | 91.54 |
| Comparative example 1 | LiNiO2-3 | 123 | 89.63 |
| Comparative example 2 | LiNiO2-4 | 118 | 84.25 |
It can be seen that from the electrical performance data of the porous nickel acid lithium anode material in table 1 by more synthesized by template
The specific discharge capacity of hole lithium nickelate positive electrode may be up to 141mAh/g, while 1C discharge-rate passes through 2000 circulation volumes
Conservation rate is still 92.16% or more；It is far from using the effect that traditional high temperature sintering methods remove template through low temperature etc.
Processes are good, this may be LiNiO during being sintered because of temperature2Structure be easy to happen caused by collapsing；In addition, using
Different templates also has an impact to the performance of porous nickel acid lithium anode material, such as: template is done using polyethylene glycol PEG6000
The effect of agent is good not as good as DMF and pyridine, this is because cannot effectively remove polyethylene glycol using low temperature plasma method.
Therefore the method for preparing anode material for lithium-ion batteries of the invention significantly improves the electric property of material prepared.
Claims (5)
1. a kind of preparation method of porous nickel acid lithium anode material, which is characterized in that specifically comprise the following steps:
(1) nickel salt is added to obtained solution A in dehydrated alcohol；
(2) aqueous slkali is added in template and stirs evenly obtained solution B；
(3) with vigorous stirring, solution B is slowly added dropwise into solution A, gained mixture is heated to 60 DEG C, and continues to stir
6h becomes light green color to the color of reaction-ure mixture from bottle green, stops stirring, is by the closed standing 5h of products therefrom room temperature
Nickel hydroxide colloidal sol can be made；
(4) by nickel hydroxide colloidal sol obtained in step (3), dynamic rotary aging 5h forms hydrogen in 80 DEG C of homogeneous reactor
Then nickel hydroxide powder is made after dry 12h in 110 DEG C of vacuum oven in nickel oxide gel；
(5) nickel hydroxide powder and lithium hydroxide powder obtained in step (4) is mixed and grind uniformly, then be added go from
Sub- water, further grinding is until gained mixture becomes blackish green dope；Vacuum by the blackish green dope of gained at 110 DEG C
Drying obtains blackish green blocks of solid for 24 hours in drying box；
(6) blackish green blocks of solid obtained in step (5) is made after powder move into dielectric barrier discharge (DBD) device into
Row low-temperature plasma handles removed template method, and in oxygen atmosphere, 200 DEG C of temperature, voltage 350V and electric current 3.0A under the conditions of handle
4h, cooled to room temperature can be prepared by the porous nickel acid lithium material.
2. the preparation method of porous nickel acid lithium anode material according to claim 1, which is characterized in that
The nickel salt, alkali, template and lithium hydroxide molar ratio be 1:5:30:1.
3. the preparation method of porous nickel acid lithium anode material according to claim 1, which is characterized in that
The nickel salt is one of anhydrous acetic acid nickel, Dehydrated nickel chloride or anhydrous nitric acid nickel.
4. the preparation method of porous nickel acid lithium anode material according to claim 1, which is characterized in that
The aqueous slkali is concentrated ammonia liquor.
5. the preparation method of porous nickel acid lithium anode material according to claim 1, which is characterized in that
The template is one of dimethylformamide, dimethyl acetamide, pyridine or piperidines.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810830978.9A CN109019702B (en) | 2018-07-26 | 2018-07-26 | Preparation method of porous lithium nickelate positive electrode material |
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| CN201810830978.9A CN109019702B (en) | 2018-07-26 | 2018-07-26 | Preparation method of porous lithium nickelate positive electrode material |
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| CN109019702A true CN109019702A (en) | 2018-12-18 |
| CN109019702B CN109019702B (en) | 2020-09-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180658A (en) * | 2022-06-28 | 2022-10-14 | 贵州梅岭电源有限公司 | Preparation method of hollow high-specific-capacity positive electrode material with directionally-arranged primary particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162196A (en) * | 1996-04-01 | 1997-10-15 | 日本电池株式会社 | Method for production of lithium nickelate positive electrode and lithium cell using said electrode |
| JPH1131532A (en) * | 1997-07-09 | 1999-02-02 | Hitachi Ltd | Lithium secondary battery |
| CN101453006A (en) * | 2007-12-03 | 2009-06-10 | 中国科学院成都有机化学有限公司 | Lithium ionic cell electrode material with micro hole construction and manufacturing method thereof |
-
2018
- 2018-07-26 CN CN201810830978.9A patent/CN109019702B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162196A (en) * | 1996-04-01 | 1997-10-15 | 日本电池株式会社 | Method for production of lithium nickelate positive electrode and lithium cell using said electrode |
| JPH1131532A (en) * | 1997-07-09 | 1999-02-02 | Hitachi Ltd | Lithium secondary battery |
| CN101453006A (en) * | 2007-12-03 | 2009-06-10 | 中国科学院成都有机化学有限公司 | Lithium ionic cell electrode material with micro hole construction and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180658A (en) * | 2022-06-28 | 2022-10-14 | 贵州梅岭电源有限公司 | Preparation method of hollow high-specific-capacity positive electrode material with directionally-arranged primary particles |
| CN115180658B (en) * | 2022-06-28 | 2024-02-27 | 贵州梅岭电源有限公司 | Preparation method of hollow high-specific-capacity positive electrode material with primary particles directionally arranged |
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