CN102683672B - Method for decreasing pH value of ternary material - Google Patents
Method for decreasing pH value of ternary material Download PDFInfo
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- CN102683672B CN102683672B CN201210002503.3A CN201210002503A CN102683672B CN 102683672 B CN102683672 B CN 102683672B CN 201210002503 A CN201210002503 A CN 201210002503A CN 102683672 B CN102683672 B CN 102683672B
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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 for reducing lithium ion anode material pH value, and in particular to one kind reduces ternary material PH
The method of value.
Background technology
Lithium ion battery is a kind of last century Mo newfound high-energy-density power supply, because lithium ion battery has energy close
Many advantages, such as degree height, high voltage platform, memory-less effect, operating temperature range width, environmentally safe.Since the advent of the world,
In being widely used to the portable electric appts such as mobile communications tool, camera, notebook computer, also contour to electric tool
Capacity power battery develops.In recent years, the yield of lithium ion battery is skyrocketed through, and application constantly expands, it has also become two
The eleventh century new high-tech product significant to national economy and people's lives.
The positive electrode that at present commercial Li-ion batteries are used is mainly cobalt acid lithium.But cobalt resource is deficient, expensive, poison
Property it is higher so that people's exigence replaces cobalt acid lithium using the novel anode material without cobalt and few cobalt.Although LiMn2O4
Positive electrode aboundresources, low price is environmentally friendly.But dissolving and the Janh- of the structural instability of LiMn2O4, manganese
The reasons such as Teller distortion cause the development of LiMn2O4 to be restricted.Ternary material combine nickel, cobalt, three elements of manganese it is each
Item advantage, with specific capacity height, has extended cycle life, has a safety feature, cheap to wait many merits to win various circles of society
Extensive concern.
Although ternary material has the advantages that numerous but the initial charge specific capacity of ternary material and platform are relatively low.And three
First material is typical layer structure, and wherein lithium ion is located at 3a positions, and transition metal ionss cobalt, nickel, manganese are located at 3b positions, oxonium ion
Positioned at 6c positions.In this lamellar compound, due to Ni2+With Li+Ionic radius be closer to, easily there is lithium in 3a positions and 3b positions
Ion and nickel ion mixing phenomenon, the chemical property which results in material is deteriorated so that material easily occurs in atmosphere analysis lithium
Phenomenon.Easily there is the precipitation that mixing phenomenon causes lithium in material internal in especially nickelic ternary material, nickel and lithium, when air it is wet
When spending larger, analysis lithium phenomenon is than more serious, in the industry temporarily without good solution.The Li of ternary material excess surface
Element, such as lithium carbonate, the soluble-salt of Lithium hydrate lithium cause the pH value of ternary material higher, and the performance of material is generated
Serious impact.PH value is too high, and the dispersion and stirring of slurry are just unfavorable for first.And the too high material of pH value can occur with aluminium foil
Chemical reaction, generates Al（OH）3, flocculent deposit is produced, to Li+Transmission produce certain inhibition. in addition while also producing
H2Gas, can make battery bulge phenomenon occur, and especially at high temperature bulge phenomenon becomes apparent from.Capacity to battery, circulates the longevity
Life, multiplying power etc. can produce serious influence.People attempt the pH value by reducing ternary material, reduce sending out for above-mentioned phenomenon
It is raw, improve the chemical property and cycle life of battery.
At present patent does not propose the pH value that ternary material is reduced by some way, for this problem, now carries
For a kind of method of reduction ternary material pH value.
The content of the invention
It is an object of the invention to provide a kind of method for reducing ternary material pH value, so as to improve the electrochemistry of material
Energy.
The present invention is employed the following technical solutions：One kind reduces ternary material pH value and obtains method, comprises the following steps：
With ternary material as raw material, deionized water or containing HCO3 -Solution material is washed, sucking filtration, by material
It is placed in multi-steps sintering in Muffle furnace.Material ball milling pulverizes to obtain powder body.
HCO of the present invention3 -Solution be NH4HCO3Solution or LiHCO3Solution etc..
The present invention is with containing HCO3 -Solution detergent when, control wash solution PH=7-14 between.
Deionized water of the present invention or containing HCO3 -Solution carry out detergent, ratio of water to material is 1：1-20：1.
Multi-steps sintering in Muffle furnace is placed in after material sucking filtration of the present invention, first paragraph sintering is warming up to 75- with 10-300 DEG C/h
95 DEG C, it is incubated 5-20h.Second segment sintering is warming up to 100-600 DEG C with 10-300 DEG C/h, temperature retention time 2-20h.
It is an advantage of the invention that：1）Material is washed with deionized, sufficiently using resource, the method is simply easy to behaviour
Make, it is with low cost.Ternary material is by adding deionized water wash so that the Li elements of ternary material excess surface are dissolved in water
Middle formation LiOH, is separated by sucking filtration with ternary material, reduces the pH value of ternary material.2）Containing HCO3 -Solution heating
Under the conditions of, water and carbon dioxide are decomposed into, it is environmentally friendly, it is pollution-free.Ternary material contains HCO by adding3 -Solution washing,
Effectively can neutralize with LiOH, reduce the pH value of ternary material. 3）Method is novel, can successfully reduce ternary material
PH value, improves the chemical property of battery.
Specific embodiment
With reference to case study on implementation, the present invention is described in further detail, and the implementation case is according to described in the content of the invention
Technical scheme implement.
Embodiment one
One kind of the present invention reduces certain commercially available 532 type, and (the atom number of nickel cobalt manganese is, nickel:Cobalt:Manganese=5:2:3) ternary material
The method of material micropowder pH value, comprises the following steps：
(i) certain commercially available 532 type ternary material micropowder of 1KG is weighed（8< D50〈12）, deionized water washed, water material
Than for 2：1.After the completion of washing, sucking filtration.
(ii) by step, (i) resulting materials are placed in multi-steps sintering in Muffle furnace body, and with 50 DEG C/h programming rates 85 are warming up to
DEG C, it is incubated 8h.
(iii) 100 DEG C -600 DEG C are warming up to again with 50 DEG C/h programming rates, are incubated 8h, wherein preferable temperature is 200 DEG C.
(iv) after the completion of sintering, material is taken out, the particle size distribution of ball mill pulverizing is 8<D50<12 powder body.
The pH value of resulting materials is as shown in table 1：
Table 1
Embodiment two
One kind of the present invention reduces certain commercially available 532 type, and (the atom number of nickel cobalt manganese is, nickel:Cobalt:Manganese=5:2:3) ternary material
The method of material micropowder pH value, comprises the following steps：
(i) certain commercially available 532 type ternary material micropowder of 1KG is weighed（8< D50〈12）In being put into beaker, NH is added4HCO3It is molten
Liquid is washed, and controls NH4HCO3PH value=11.0 of solution, NH4HCO3Solution and material ratio are 2：1.After the completion of washing, take out
Filter.
(ii) by step, (i) resulting materials are placed in multi-steps sintering in Muffle furnace body, and with 50 DEG C/h programming rates 85 are warming up to
DEG C, it is incubated 8h.
(iii) 100 DEG C -600 DEG C are warming up to again with 50 DEG C/h programming rates, are incubated 8h, wherein preferable temperature is 200 DEG C.
(iv) after the completion of sintering, material is taken out, the particle size distribution of ball mill pulverizing is 8<D50<12 powder body.
The pH value of resulting materials is as shown in table 2:
Table 2
Claims (1)
1. it is a kind of reduce ternary material pH value method, it is characterised in that：With ternary material as raw material, with containing HCO3 -Solution pair
Material is washed, sucking filtration, and material is placed in into multi-steps sintering in Muffle furnace, and material ball milling pulverizes to obtain powder body；It is described containing HCO3 -'s
Solution is NH4HCO3Solution or LiHCO3Solution；With containing HCO3 -Solution detergent when, control wash solution pH=7-14
Between；Multi-steps sintering in Muffle furnace is placed in, first paragraph sintering is warming up to 75-95 DEG C, is incubated 5-20h with 10-300 DEG C/h；Second
Section sintering is warming up to 100-600 DEG C with 10-300 DEG C/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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| CN102683672B true CN102683672B (en) | 2017-04-19 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| CN111554919B (en) * | 2019-02-12 | 2022-04-22 | 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908621A (en) * | 2010-07-14 | 2010-12-08 | 白洁明 | Method for modifying anode active material of lithium ion battery |
| 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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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101908621A (en) * | 2010-07-14 | 2010-12-08 | 白洁明 | Method for modifying anode active material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| Washing Effect of a LiNi0.83Co0.15Al0.02O2 Cathode in Water;Jisuk Kim等;《Electrochemical and Solid-State Letters》;20051121;第9卷(第1期);全文 * |
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