CN102683672A - Method for decreasing pH value of ternary material - Google Patents
Method for decreasing pH value of ternary material Download PDFInfo
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- CN102683672A CN102683672A CN2012100025033A CN201210002503A CN102683672A CN 102683672 A CN102683672 A CN 102683672A CN 2012100025033 A CN2012100025033 A CN 2012100025033A CN 201210002503 A CN201210002503 A CN 201210002503A CN 102683672 A CN102683672 A CN 102683672A
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- ternary material
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- ternary
- hco
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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 method for decreasing a pH value of a ternary material. The method comprises the following steps of: washing the ternary material which serves as a raw material by using deionized water or a solution which contains HCO3<->; performing suction filtration on the material; placing the material into a muffle furnace, and performing multi-step sintering; and ball-milling and grinding the material, and thus obtaining powder. The method has the advantages that 1) the material is washed by using the deionized water, resources are fully utilized, and the method is simple, easy to operate and low in cost; 2) when heated, the solution which contains the HCO3<-> is decomposed into water and carbon dioxide, which are environment-friendly and pollution-free; and 3) the method is novel, the pH value of the ternary material can be successfully decreased, and the electrochemical performance of a battery is improved.
Description
Technical field
The present invention relates to a kind of method that reduces the lithium ion anode material pH value, be specifically related to a kind of method that reduces the ternary material pH value.
Background technology
Lithium ion battery is newfound a kind of high-energy-density power supply of last century Mo, plurality of advantages such as energy density height, high voltage platform, memory-less effect, operating temperature range are wide because lithium ion battery has, environmentally safe.Since coming out, be widely used in also developing in the portable electric appts such as mobile communications tool, camera, notebook computer to high power capacity electrokinetic cells such as electric tools.In recent years, the output of lithium ion battery rapidly increases, and application constantly enlarges, become 21st century to national economy and the significant new high-tech product of people's lives.
The positive electrode of commercial Li-ion batteries use at present mainly is a cobalt acid lithium.But cobalt resource is deficient, costs an arm and a leg, and toxicity is higher, makes people's exigence use the novel anode material of no cobalt and few cobalt to replace cobalt acid lithium.Though the manganate cathode material for lithium aboundresources, low price, environmentally friendly.But reasons such as the dissolving of the structural instability of LiMn2O4, manganese and Janh-Teller distortion make the development of LiMn2O4 be restricted.Ternary material has combined each item advantage of nickel, cobalt, manganese three elements, has the specific capacity height, has extended cycle life, security performance is good, and numerous advantages such as cheap have won the extensive concern of various circles of society.
Though but ternary material has the initial charge specific capacity and the platform of numerous advantage ternary materials lower.And ternary material is typical layer structure, and wherein lithium ion is positioned at the 3a position, and transition metal ions cobalt, nickel, manganese are positioned at the 3b position, and oxonium ion is positioned at the 6c position.In this lamellar compound, because Ni
2+With Li
+Ionic radius more approaching, lithium ion and nickel ion mixing phenomenon appear in 3a position and 3b position easily, the chemical property variation that this has caused material makes material in air, be prone to analyse the lithium phenomenon.Especially nickelic ternary material, nickel and lithium are prone to take place the mixing phenomenon at material internal and cause separating out of lithium, and when air humidity was big, it was more serious analysing the lithium phenomenon, does not temporarily have good solution in the industry.The Li element that ternary material surface is unnecessary makes that like the soluble-salt of lithiums such as lithium carbonate, lithium hydroxide the pH value of ternary material is higher, the performance of material has been produced seriously influence.PH value is too high, at first just is unfavorable for the dispersion and the stirring of slurry.And the too high material of pH value can with aluminium foil generation chemical reaction, generate Al (OH)
3, produce flocculent deposit, to Li
+Transmission produce certain inhibition. also produce H in addition simultaneously
2Gas can make battery bulge phenomenon occur, and especially at high temperature bulge phenomenon is more obvious.To the capacity of battery, cycle life, multiplying power etc. all can produce serious influence.People attempt reducing the generation of above-mentioned phenomenon through reducing the pH value of ternary material, improve the chemical property and the cycle life of battery.
Patent does not propose to this problem, a kind of method that reduces the ternary material pH value to be provided at present through reducing the pH value of ternary material someway at present.
Summary of the invention
The object of the present invention is to provide a kind of method that reduces the ternary material pH value, thereby improve the chemical property of material.
The present invention adopts following technical scheme: a kind of reduction ternary material pH value gets method, may further comprise the steps:
With the ternary material is raw material, perhaps contains HCO with deionized water
3 -Solution material is washed, suction filtration places the Muffle furnace multi-steps sintering with material.The material ball milling pulverize powder.
HCO according to the invention
3 -Solution be NH
4HCO
3Solution or LiHCO
3Solution etc.
The present invention is with containing HCO
3 -The solution washing material time, control wash solution PH=7-14 between.
The present invention is with deionized water or contain HCO
3 -Solution carry out detergent, ratio of water to material is 1:1-20:1.
Material suction filtration of the present invention is placed on multi-steps sintering in the Muffle furnace, and first section sintering is warming up to 75-95 ℃ with 10-300 ℃/h, insulation 5-20h.Second section sintering is warming up to 100-600 ℃ with 10-300 ℃/h, temperature retention time 2-20h.
Advantage of the present invention is: 1) uses the deionized water wash material, utilizes resource fully, and the simple easy operating of this method, with low cost.Ternary material makes the unnecessary Li element in ternary material surface be dissolved in the water and forms LiOH through adding deionized water wash, separates with ternary material through suction filtration, reduces the pH value of ternary material.2) contain HCO
3 -Solution the heating condition under, be decomposed into water and carbon dioxide, environmentally friendly, pollution-free.Ternary material contains HCO through adding
3 -Solution washing, can be effectively and the LiOH neutralization, reduce the pH value of ternary material.3) method is novel, and the pH value of reduction ternary material that can be successful improves the chemical property of battery.
Embodiment
Below in conjunction with case study on implementation the present invention is done further detailed description, this case study on implementation is implemented according to the described technical scheme of summary of the invention.
Embodiment one
A kind of certain commercially available 532 type of reduction of the present invention (the atom number of nickel cobalt manganese is nickel: cobalt: the method for ternary material micro mist pH value of manganese=5:2:3) may further comprise the steps:
(1) takes by weighing certain commercially available 532 type ternary material micro mist (8 of 1KG<d
5012), and washing with deionized water, ratio of water to material is 2:1.After washing is accomplished, suction filtration.
(2) places multi-steps sintering in the Muffle furnace body of heater with step (4) gained material, is warming up to 85 ℃ with 50 ℃/h programming rate, insulation 8h.
(3) is warming up to 100 ℃-600 ℃ with 50 ℃/h programming rate again, insulation 8h, and wherein preferred temperature is 200 ℃.
After the (4) sintering is accomplished, material is taken out, the particle size distribution of ball mill grinding is 8<d
50<12 powder.
The pH value of gained material is as shown in table 1:
Table 1
Embodiment two
A kind of certain commercially available 532 type of reduction of the present invention (the atom number of nickel cobalt manganese is nickel: cobalt: the method for ternary material micro mist pH value of manganese=5:2:3) may further comprise the steps:
(1) takes by weighing certain commercially available 532 type ternary material micro mist (8 of 1KG<d
5012) and put into beaker, add NH
4HCO
3Solution washs, control NH
4HCO
3The pH value of solution=11.0, NH
4HCO
3Solution and material are than being 2:1.After washing is accomplished, suction filtration.
(2) places multi-steps sintering in the Muffle furnace body of heater with step (4) gained material, is warming up to 85 ℃ with 50 ℃/h programming rate, insulation 8h.
(3) is warming up to 100 ℃-600 ℃ with 50 ℃/h programming rate again, insulation 8h, and wherein preferred temperature is 200 ℃.
After the (4) sintering is accomplished, material is taken out, the particle size distribution of ball mill grinding is 8<d
50<12 powder.
The pH value of gained material is as shown in table 2:
Table 2
Claims (5)
1. a method that reduces the ternary material pH value is characterized in that: be raw material with the ternary material, perhaps contain HCO with deionized water
3 -Solution material is washed, suction filtration places the Muffle furnace multi-steps sintering with material, the material ball milling pulverize powder.
2. a kind of method that reduces the ternary material pH value according to claim 1 is characterized in that: contain HCO
3 -Solution be NH
4HCO
3Solution or LiHCO
3Solution.
3. a kind of method that reduces the ternary material pH value according to claim 1 is characterized in that: with containing HCO
3 -The solution washing material time, control wash solution PH=7-14 between.
4. a kind of method that reduces the ternary material pH value according to claim 1 is characterized in that: perhaps contain HCO with deionized water
3 -Solution carry out detergent, ratio of water to material is 1:1-20:1.
5. a kind of method that reduces the ternary material pH value according to claim 1 is characterized in that: place multi-steps sintering in the Muffle furnace, first section sintering is warming up to 75-95 ℃ with 10-300 ℃/h, insulation 5-20h;
Second section sintering is warming up to 100-600 ℃ with 10-300 ℃/h, temperature retention time 2-20h.
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| CN201210002503.3A CN102683672B (en) | 2012-01-06 | 2012-01-06 | Method for decreasing pH value of ternary material |
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| CN102683672A true CN102683672A (en) | 2012-09-19 |
| CN102683672B CN102683672B (en) | 2017-04-19 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337614A (en) * | 2013-05-20 | 2013-10-02 | 深圳市贝特瑞新能源材料股份有限公司 | Method for modification of lithium ion battery anode material |
| CN103400978A (en) * | 2013-08-01 | 2013-11-20 | 奇瑞汽车股份有限公司 | Method for modifying lithium nickel manganese oxide material, lithium nickel manganese oxide material and lithium ion battery |
| CN103825016A (en) * | 2014-02-13 | 2014-05-28 | 宁波金和新材料股份有限公司 | Nickelic cathode material rich in lithium and preparation method thereof |
| CN105810929A (en) * | 2014-12-31 | 2016-07-27 | 北京当升材料科技股份有限公司 | Treatment method for reducing residual alkalis on surface of high nickel material |
| CN108063245A (en) * | 2017-10-30 | 2018-05-22 | 广东邦普循环科技有限公司 | A kind of method for reducing rich nickel ternary material surface lithium impurity |
| CN111554919A (en) * | 2019-02-12 | 2020-08-18 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method thereof and sodium ion battery |
| CN111653761A (en) * | 2019-03-04 | 2020-09-11 | 东莞东阳光科研发有限公司 | Preparation method of high-nickel cathode material with improved washing |
| CN114023949A (en) * | 2021-09-22 | 2022-02-08 | 上海超碳石墨烯产业技术有限公司 | Method for reducing LiOH content on surface of ternary material |
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| CN101908621A (en) * | 2010-07-14 | 2010-12-08 | 白洁明 | Method for modifying anode active material of lithium ion battery |
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| CN102239118A (en) * | 2008-12-04 | 2011-11-09 | 户田工业株式会社 | Powder of lithium complex compound particles, method for producing the same, and nonaqueous electrolyte secondary cell |
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Non-Patent Citations (1)
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9440861B2 (en) | 2013-05-20 | 2016-09-13 | Shenzhen Btr New Energy Materials Inc. | Method for modification of lithium ion battery positive electrode material |
| CN103337614B (en) * | 2013-05-20 | 2015-11-25 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of method of modification of lithium ion battery anode material |
| CN103337614A (en) * | 2013-05-20 | 2013-10-02 | 深圳市贝特瑞新能源材料股份有限公司 | Method for modification of lithium ion battery anode material |
| CN103400978A (en) * | 2013-08-01 | 2013-11-20 | 奇瑞汽车股份有限公司 | Method for modifying lithium nickel manganese oxide material, lithium nickel manganese oxide material and lithium ion battery |
| CN103825016A (en) * | 2014-02-13 | 2014-05-28 | 宁波金和新材料股份有限公司 | Nickelic cathode material rich in lithium and preparation method thereof |
| CN103825016B (en) * | 2014-02-13 | 2016-09-07 | 宁波金和锂电材料有限公司 | A kind of rich nickelic positive electrode of lithium and preparation method thereof |
| CN105810929A (en) * | 2014-12-31 | 2016-07-27 | 北京当升材料科技股份有限公司 | Treatment method for reducing residual alkalis on surface of high nickel material |
| CN108063245A (en) * | 2017-10-30 | 2018-05-22 | 广东邦普循环科技有限公司 | A kind of method for reducing rich nickel ternary material surface lithium impurity |
| CN108063245B (en) * | 2017-10-30 | 2020-06-30 | 广东邦普循环科技有限公司 | Method for reducing lithium impurities on surface of nickel-rich ternary material |
| CN111554919A (en) * | 2019-02-12 | 2020-08-18 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method thereof and sodium ion battery |
| CN111653761A (en) * | 2019-03-04 | 2020-09-11 | 东莞东阳光科研发有限公司 | Preparation method of high-nickel cathode material with improved washing |
| CN111653761B (en) * | 2019-03-04 | 2023-08-04 | 东莞东阳光科研发有限公司 | Preparation method of high-nickel positive electrode material with improved water washing |
| CN114023949A (en) * | 2021-09-22 | 2022-02-08 | 上海超碳石墨烯产业技术有限公司 | Method for reducing LiOH content on surface of ternary material |
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