CN109721110A - A method of obtaining nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles - Google Patents
A method of obtaining nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles Download PDFInfo
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- CN109721110A CN109721110A CN201811648632.3A CN201811648632A CN109721110A CN 109721110 A CN109721110 A CN 109721110A CN 201811648632 A CN201811648632 A CN 201811648632A CN 109721110 A CN109721110 A CN 109721110A
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- nickel cobalt
- cobalt manganese
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- nickel
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention relates to the recycling of lithium battery, a kind of specifically method that nickel cobalt manganese hydroxide is obtained from the active material that waste lithium cell recycles.Specially 1) by the nickel cobalt manganese leachate obtained by waste power lithium battery at -20 DEG C~10 DEG C 0.1~5h of insulated and stirred, filter out the crystal salt of precipitation, obtain nickel cobalt manganese sulfate liquor；2) adjusting nickel cobalt manganese total ion concentration in above-mentioned nickel cobalt manganese sulfate liquor is 1~3mol/L；3) add ammonium hydroxide to carry out complex reaction to system pH=8~10 into nickel cobalt manganese sulfate liquor after adjusting, then adjust reaction system pH=10~12 again, be aged after adjusting, the Washing of Filter Cake of filtering is dried to obtain nickel-cobalt-manganese ternary element complex hydroxide.After the present invention operates the nickel cobalt manganese leachate of recycling by crystallization except impurity salt, it is satisfied the nickel cobalt mn sulphate mixed solution of anode material of lithium battery precursor preparation requirement, is had important practical significance to the recycling of valuable metal.
Description
Technical field
The present invention relates to the recycling of lithium battery, specifically a kind of to obtain from the active material that waste lithium cell recycles
The method of nickel cobalt manganese hydroxide.
Background technique
The continuous consumption of continuous improvement and natural resources recently as people's environmental protection consciousness, it is environmental-friendly
Lithium battery be developed and be used widely.Lithium battery have operating voltage is high, small in size, light weight, energy height,
Low pollution, the advantages that having extended cycle life, it has also become the absolute master of the target markets such as mobile phone, digital product, portable DVD player
Power product.Currently, China has become largest production, consumption and the exported country of lithium battery.However, huge battery production consumption
Bring the surprising refuse battery of number.Although influence of the lithium battery to environment is relatively small, lithium relative to one-shot battery
The substances such as the positive and negative electrode material of battery, electrolyte still have very big harm to the health of environment and the mankind.It is reported that the U.S.
Lithium battery is classified as a kind of battery including the poisonous and harmful property such as inflammability, Leaching, corrosivity, reactivity, is each
It include the most battery of toxicant in class battery.For a long time, China does not carry out special place to largely discarded lithium battery
Reason, is substantially carried out landfill stabilization.Although there are also the recovery processing that some enterprises have started waste lithium cell, by
In the reason of the technology and economy etc., the waste lithium cell rate of recovery is also very low at present, less than 2%, causes huge danger to environment
Evil, while being also a kind of waste to resource.
The patent of current research waste and old lithium ion battery renewable resources and registration are also more, mainly have hydrometallurgic recovery and do
Method recycling, wherein hydrometallurgic recovery is current main recovery method.In hydrometallurgic recovery technology, mainly by acidleach, removal of impurities,
The processes such as co-precipitation recycle the active material in lithium battery.The method that wherein co-precipitation step mainly uses is complexing
The precipitation method.But the nickel cobalt manganese leachate that existing mainstream lithium electricity recovery processing technology obtains cannot be carried out directly as nickel cobalt manganese source
The preparation of nickel cobalt manganese hydroxide, needs to blend and is used in mixed way in the nickel cobalt manganese sulfate liquor largely newly prepared, and gives lithium
The recycling and reusing of battery is made troubles, and the resource utilization efficiency of waste lithium cell active material is reduced.
Summary of the invention
Nickel cobalt manganese hydroxide is obtained from the active material that waste lithium cell recycles it is an object of that present invention to provide a kind of
Method.
To achieve the above object, the present invention uses technical solution:
A method of the acquisition nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles, 1) it will be by waste and old
The nickel cobalt manganese leachate that dynamic lithium battery obtains insulated and stirred 0.1-5h at -20 DEG C -10 DEG C, filters out the crystal salt of precipitation, obtains
To nickel cobalt manganese sulfate liquor；
2) adjusting nickel cobalt manganese total ion concentration in above-mentioned nickel cobalt manganese sulfate liquor is 1-3mol/L；
3) adjust after into nickel cobalt manganese sulfate liquor plus ammonium hydroxide to system pH=8-10 carry out complex reaction, then again
Reaction system pH=10-12 is adjusted, is aged after adjusting, the Washing of Filter Cake of filtering is dried to obtain the compound hydrogen-oxygen of nickel-cobalt-manganese ternary element
Compound.
Reaction system pH=10-12 is adjusted after the step 3) complex reaction, by 40-80 DEG C under n 2 atmosphere of reaction solution
Ageing reaction 5-50h, the Washing of Filter Cake of filtering are dried to obtain nickel-cobalt-manganese ternary element complex hydroxide.
Step 1) the nickel cobalt manganese leachate be obtained according to existing way, be sulfur acid nickel, cobaltous sulfate, manganese sulfate,
The mixed solution of sodium sulphate.
It is 1-8:1-5:1- that the step 2), which adjusts Ni, Co, Mn elemental mole ratios example in above-mentioned nickel cobalt manganese sulfate liquor,
3；Wherein, Ni, Co, Mn member in solution are adjusted by adding nickel sulfate, cobaltous sulfate and manganese sulfate into nickel cobalt manganese sulfate liquor
Element mole.
Advantage for present invention:
(1) after the present invention operates the nickel cobalt manganese leachate of recycling by crystallization except impurity salt, it is satisfied lithium battery
The nickel cobalt mn sulphate mixed solution that positive electrode material precursor preparation requires there is important reality to anticipate the recycling of valuable metal
Justice.
(2) present invention is using above-mentioned crystallization except the operation of impurity salt obtains nickel cobalt mn sulphate mixed solution as main
Nickel cobalt manganese source carries out complex coprecipitation and the nickel cobalt manganese hydroxide for meeting anode material of lithium battery presoma requirement is made.
Detailed description of the invention
Fig. 1 is the acquisition nickel cobalt manganese hydroxide provided in an embodiment of the present invention from the active material that waste lithium cell recycles
The process flow chart of object.
Fig. 2 provides the SEM figure for obtaining nickel cobalt manganese hydroxide for the embodiment of the present invention.
Specific embodiment
Meticulously invention has been described comprehensively for embodiment, but protection scope of the present invention is not limited to following reality
Example is applied, under the premise of not departing from basic conception of the present invention, can also make related process improvement, these are all guarantors of the invention
Protect range.
Embodiment 1:
As shown in Figure 1, according to existing recovery method by 10 section waste power lithium batteries by broken, pyrolysis, acidleach,
After the operation such as removal of impurities, nickel cobalt manganese leachate 2300g is obtained, is cooled to -10 DEG C of stirring heat preservation 1h, 260g knot is precipitated in filtration and washing
Brilliant salt (sal glauberi), filtrate 2040g, and the nickel that nickel sulfate, cobaltous sulfate, manganese sulfate adjust filtrate is added in backward filtrate
Cobalt manganese element molar ratio is 5:2:3, nickel cobalt manganese mixed salt total concentration 2.0mol/L in filtrate.Liquid in filtrate after adjustment is added
3Mol/L ammonium hydroxide is complexed, and regulation system pH=9.5, adds 4Mol/L sodium hydroxide solution after adjusting into complex liquid again
Adjust pH=10.8；20h is reacted into 60 DEG C of ageings of reaction solution after adjusting, filtration washing is dry, obtains ternary precursor nickel cobalt manganese
Complex hydroxide 152.0g (referring to fig. 2).
1 physical index of table
Seen from table 1, recycling gained ternary precursor physical index can reach the use of anode material of lithium battery presoma
It is required that.
Embodiment 2:
By 10 section waste power lithium batteries after the operation such as broken, pyrolysis, acidleach, removal of impurities, nickel cobalt manganese leachate is obtained
2250g is cooled to -10 DEG C of stirring heat preservation 0.5h, and filtration and washing obtains 240g sal glauberi, and filtrate 2010g adds sulfuric acid
Nickel, cobaltous sulfate, manganese sulfate adjustment nickel cobalt manganese element ratio are 1:1:1, nickel cobalt manganese mixed salt concentration 2.0mol/L.Nickel cobalt manganese is mixed
Salting liquid adds 3Mol/L ammonium hydroxide to be complexed, and adjusts pH=9.8, and complex liquid adds 4Mol/L sodium hydroxide solution to adjust pH=10.5.
30h is reacted into 60 DEG C of ageings of reaction solution, filtration washing is dry, obtains ternary precursor nickel cobalt manganese composite hydroxide 148.0g.
2 physical index of table
As can be seen from Table 2, recycling gained ternary precursor physical index can reach the use of anode material of lithium battery presoma
It is required that.
Embodiment 3:
By 10 section waste power lithium batteries after the operation such as broken, pyrolysis, acidleach, removal of impurities, nickel cobalt manganese leachate is obtained
2150g, is cooled to -5 DEG C of stirrings heat preservation 2h, filtration and washing, obtains 250g sal glauberi, filtrate 1900g, addition nickel sulfate,
Cobaltous sulfate, manganese sulfate adjustment nickel cobalt manganese element ratio are 5:2:3, nickel cobalt manganese mixed salt concentration 2.0mol/L.Nickel cobalt manganese mixed salt is molten
Liquid adds 3Mol/L ammonium hydroxide to be complexed, and adjusts pH=9.6, and complex liquid adds 4Mol/L sodium hydroxide solution to adjust pH=10.6.It will be anti-
60 DEG C of ageing reaction 40h of liquid are answered, filtration washing is dry, obtains ternary precursor nickel cobalt manganese composite hydroxide 150.0g.
3 physical index of table
Seen from table 3, recycling gained ternary precursor physical index can reach the use of anode material of lithium battery presoma
It is required that.
Claims (4)
1. a kind of method for obtaining nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles, it is characterised in that:
1) by the nickel cobalt manganese leachate obtained by waste power lithium battery at -20 DEG C~10 DEG C 0.1~5h of insulated and stirred, filter out
The crystal salt of precipitation obtains nickel cobalt manganese sulfate liquor；
2) adjusting nickel cobalt manganese total ion concentration in above-mentioned nickel cobalt manganese sulfate liquor is 1~3mol/L；
3) add ammonium hydroxide to carry out complex reaction to system pH=8~10 into nickel cobalt manganese sulfate liquor after adjusting, then adjust again
Reaction system pH=10~12 are aged after adjusting, and the Washing of Filter Cake of filtering is dried to obtain nickel-cobalt-manganese ternary element complex hydroxide.
2. the method according to claim 1 that nickel cobalt manganese hydroxide is obtained from the active material that waste lithium cell recycles,
It is characterized by: reaction system pH=10~12 are adjusted after the step 3) complex reaction, by reaction solution in N240 under atmosphere~
5~50h is reacted in 80 DEG C of ageings, and the Washing of Filter Cake of filtering is dried to obtain nickel-cobalt-manganese ternary element complex hydroxide.
3. the method according to claim 1 that nickel cobalt manganese hydroxide is obtained from the active material that waste lithium cell recycles,
It is characterized by: step 1) the nickel cobalt manganese leachate is the mixed solution of sulfur acid nickel, cobaltous sulfate, manganese sulfate, sodium sulphate.
4. the method according to claim 1 that nickel cobalt manganese hydroxide is obtained from the active material that waste lithium cell recycles,
It is characterized by: it is 1-8:1-5 that the step 2), which adjusts Ni, Co, Mn elemental mole ratios example in above-mentioned nickel cobalt manganese sulfate liquor:
1-3。
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| CN201811648632.3A CN109721110A (en) | 2018-12-30 | 2018-12-30 | A method of obtaining nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285738A (en) * | 2011-08-15 | 2011-12-21 | 湖南邦普循环科技有限公司 | Treatment method of high-salinity waste water in waste lithium battery recovering industry |
| CN103943847A (en) * | 2014-04-21 | 2014-07-23 | 中信国安盟固利电源技术有限公司 | Method for preparing nickel-cobalt-manganese ternary material precursor |
| CN104261607A (en) * | 2014-09-26 | 2015-01-07 | 浙江华友钴业股份有限公司 | Processing method of complex raffinate |
| CN106505272A (en) * | 2016-12-12 | 2017-03-15 | 江西赣锋锂业股份有限公司 | A kind of processing method of anode material of lithium battery waste material |
| CN107117661A (en) * | 2017-05-26 | 2017-09-01 | 金川集团股份有限公司 | The method that nickel cobalt manganese prepares ternary hydroxide in the waste and old lithium ion battery reclaimed using liquid phase method |
-
2018
- 2018-12-30 CN CN201811648632.3A patent/CN109721110A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285738A (en) * | 2011-08-15 | 2011-12-21 | 湖南邦普循环科技有限公司 | Treatment method of high-salinity waste water in waste lithium battery recovering industry |
| CN103943847A (en) * | 2014-04-21 | 2014-07-23 | 中信国安盟固利电源技术有限公司 | Method for preparing nickel-cobalt-manganese ternary material precursor |
| CN104261607A (en) * | 2014-09-26 | 2015-01-07 | 浙江华友钴业股份有限公司 | Processing method of complex raffinate |
| CN106505272A (en) * | 2016-12-12 | 2017-03-15 | 江西赣锋锂业股份有限公司 | A kind of processing method of anode material of lithium battery waste material |
| CN107117661A (en) * | 2017-05-26 | 2017-09-01 | 金川集团股份有限公司 | The method that nickel cobalt manganese prepares ternary hydroxide in the waste and old lithium ion battery reclaimed using liquid phase method |
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