CN102134642A - Method for improving metal leaching rate in waste lithium ion batteries by controlling oxidation-reduction potential - Google Patents
Method for improving metal leaching rate in waste lithium ion batteries by controlling oxidation-reduction potential Download PDFInfo
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- CN102134642A CN102134642A CN2011100504071A CN201110050407A CN102134642A CN 102134642 A CN102134642 A CN 102134642A CN 2011100504071 A CN2011100504071 A CN 2011100504071A CN 201110050407 A CN201110050407 A CN 201110050407A CN 102134642 A CN102134642 A CN 102134642A
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- Prior art keywords
- lithium ion
- leaching
- ion batteries
- lithium
- waste lithium
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for improving the metal leaching rate in waste lithium ion batteries by controlling oxidation-reduction potential, which comprises the following steps of: (1) removing shells of the waste lithium ion batteries; (2) preparing a leaching medium from the following components in a weight/volume ratio: 3.0g/L of (NH4)2SO4, 0.1g/L of KCl, 0.5g/L of K2HPO4, 0.5g/L of MgSO4.7H2O, 0.01g/L of Ca(NO3)2, and 25g/L of FeSO4.7H2O, and ensuring the pH of the leaching medium is 2.0; and (3) inoculating acidithiobacillus ferrooxidans in an inoculums concentration of 10 percent. The invention has the advantages that: the consumption of nutrients of the mediums can be reduced, the leaching efficiency of lithium cobaltoxide is greatly improved, the consumption of FeSO4 in a 9K medium of 44.8g/L is reduced to 25g/L, the leaching rates of cobalt and lithium can be respectively improved to 97 percent and 80 percent, and a new technical method with low cost and high leaching efficiency is provide for recovering valuable metals in the waste lithium ion batteries, and is a treatment method with good application prospect.
Description
Technical field
The present invention relates to a kind of method that improves metal leaching rate in the waste and old lithium ion battery, relate in particular to a kind of method that redox potential improves metal leaching rate in the waste and old lithium ion battery of regulating and control.
Background technology
Cobalt acid lithium is the most sophisticated anode material of lithium battery at present, as mobile phone, and digital camera, the positive electrode material of the battery of notebook at short notice, particularly has the advantage of not replacing in the communication field of batteries.China is the largest production state of lithium ion battery in the world and consumes state.Valuable metal content such as cobalt and lithium are than higher in the discarded lithium ion battery, and contain chemical substances such as cobalt acid lithium, lithium hexafluoro phosphate in the lithium ion battery, can work the mischief to environment.Discarded anode material for lithium-ion batteries is the industrial refuse product of a kind of 45-55% of containing cobalt, 2-4% lithium, therefore the valuable rare metal Co and the Li that reclaim in the waste lithium ion cell anode material have very important significance for reducing environmental pollution and resource recovery, also have quite high recovery economic worth.
The method that reclaims lithium ion battery at present has high-temperature calcination, wet method acid immersion and biological the leaching.Biological leaching-out technique has been successfully applied to that some are low-grade, in the extraction in indissoluble ore deposit, the domestic bibliographical information of having seen the cobalt in the discarded lithium ion battery of employing bioleaching stripping in the recent period, external reported also that recently biological lixiviation process reclaims the cobalt in the discarded lithium ion battery and the laboratory study of lithium, biological leaching-out technique has power consumption and lacks, clear superiorities such as organic efficiency height, but the major influence factors in the reaction process, especially the solution oxide reduction potential is not well controlled, thereby has restricted the effect that metal leaches in the discarded lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of method that redox potential improves metal leaching rate in the waste and old lithium ion battery of regulating and control, thereby reduced substratum nutritive substance consumption, improved cobalt acid lithium leaching efficiency.
The present invention is achieved like this, and method steps is:
(1) will discard lithium ion battery and remove decapsidate, take out aluminium foil, cell positive material will be crushed to 100 ~ 200 orders, get battery powder cobalt acid lithium;
(2) leach substratum by weight volume ratio be: (NH
4)
2SO
43.0g/L, KCl0.1 g/L, K
2HPO
40.5g/L, MgSO
4 .7H
2O 0.5g/L, Ca (NO
3)
20. 01g/L, FeSO
4.7H
2O 25g/L, pH are 2.0;
(3) have a liking for the ferrous thiobacillus of acid oxidase by the inoculation of 10% inoculum size, 1% solid-to-liquid ratio adding granularity is 100 ~ 200 purpose cobalts acid lithium powder and adds metal ion Cu
2+Or Ag
+, temperature is controlled to be 30 ℃ of constant temperature, and rotating speed is 180r/min shaking culture in constant temperature vibration case, utilizes redox electrode to measure redox potential, and control infusion solution redox potential is more than 400mV.
Technique effect of the present invention is: utilize the present invention can reduce the consumption of substratum nutritive substance, improve the leaching efficiency of cobalt acid lithium greatly, by FeSO in the 9K substratum
4Consumption 44.8g/L reduce to 25g/L, leach after 3 days, the leaching yield of cobalt and lithium can bring up to 97% and 80% respectively, for the recovery of valuable metal in the waste and old lithium ion battery provides a new cost to hang down the high technological method of leaching efficiency, is a kind of treatment process that application prospect is arranged very much.
Embodiment
The influence that embodiment 1 cupric ion leaches cobalt acid lithium
The waste lithium ion cell anode material that the present invention is used: get waste and old lithium ion battery, remove metal shell and aluminium foil,, get the battery powder to cell positive material crushing and screening to 100 ~ 200 orders.
Bacterial classification: have a liking for the ferrous thiobacillus of acid oxidase
Substratum: this substratum is mixed by A liquid and B liquid and forms:
A liquid: (NH
4)
2SO
43.0g, KCl0.1 g, K
2HPO
40.5g, MgSO
4 .7H
2O 0.5g, Ca (NO
3)
20. 01g, distilled water 500mL, 121 ℃ of sterilization 20min;
B liquid: FeSO
4.7H
2O 25g distilled water 500mL is with millipore filtration (diameter 0.22um) filtration sterilization.
Get two same 250mL Erlenmeyer flasks through the high-temperature steam sterilization, add the substratum that 200mL configures, then by the inoculation of 10% inoculum size, 1% solid-to-liquid ratio adds 2g cobalt acid lithium powder, and one of them adds the Cu of 0.005g/L again
2+Erlenmeyer flask is placed 30 ℃ constant temperature oscillator, under the 180r/min condition, carry out shaking culture.Measure ORP in the culture medium solution every day by the ORP electrode, and measure wherein cobalt and lithium concentration.The result shows, carries out the mensuration of redox potential at identical extraction time, adds the copper ion solution redox potential and improves about 100mV; Added cupric ion and leached after 3 days, the leaching yield of cobalt and lithium can reach 97% and 80% respectively.
The influence that embodiment 2 silver ionss leach cobalt acid lithium
The waste lithium ion cell anode material that the present invention is used: get waste and old lithium ion battery, remove metal shell and aluminium foil,, get the battery powder to cell positive material crushing and screening to 100 ~ 200 orders.
Bacterial classification: have a liking for the ferrous thiobacillus of acid oxidase
Substratum: this substratum is mixed by A liquid and B liquid and forms:
A liquid: (NH
4)
2SO
43.0g, KCl0.1 g, K
2HPO
40.5g, MgSO
4 .7H
2O 0.5g, Ca (NO
3)
20. 01g, distilled water 500mL, 121 ℃ of sterilization 20min;
B liquid: FeSO
4.7H
2O 25g, distilled water 500mL is with millipore filtration (diameter 0.22um) filtration sterilization.
Get two same 250mL Erlenmeyer flasks through the high-temperature steam sterilization, add the substratum that 200mL configures, then by the inoculation of 10% inoculum size, 1% solid-to-liquid ratio adds 2g cobalt acid lithium powder, and one of them adds the Ag of 0.005g/L again
+, Erlenmeyer flask is placed 30 ℃ constant temperature oscillator, under the 180r/min condition, carry out shaking culture.Measure ORP in the culture medium solution every day by the ORP electrode, and measure wherein cobalt and lithium concentration.The result shows, carries out the mensuration of redox potential at identical extraction time, adds the silver ion solution redox potential and improves about 100mV; Added silver ions and leached after 3 days, the leaching yield of cobalt and lithium can reach 97% and 80% respectively.
Claims (1)
1. regulate and control the method that redox potential improves metal leaching rate in the waste and old lithium ion battery for one kind, it is characterized in that method steps is:
(1) will discard lithium ion battery and remove decapsidate, take out aluminium foil, cell positive material will be crushed to 100 ~ 200 orders, get battery powder cobalt acid lithium;
(2) leach substratum by weight volume ratio be: (NH
4)
2SO
43.0g/L, KCl0.1 g/L, K
2HPO
40.5g/L, MgSO
4 .7H
2O 0.5g/L, Ca (NO
3)
20. 01g/L, FeSO
4.7H
2O 25g/L, pH are 2.0;
(3) have a liking for the ferrous thiobacillus of acid oxidase by the inoculation of 10% inoculum size, 1% solid-to-liquid ratio adding granularity is 100 ~ 200 purpose cobalts acid lithium powder and adds metal ion Cu
2+Or Ag
+, temperature is controlled to be 30 ℃ of constant temperature, and rotating speed is 180r/min shaking culture in constant temperature vibration case, utilizes redox electrode to measure redox potential, and control infusion solution redox potential is more than 400mV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100504071A CN102134642A (en) | 2011-03-03 | 2011-03-03 | Method for improving metal leaching rate in waste lithium ion batteries by controlling oxidation-reduction potential |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100504071A CN102134642A (en) | 2011-03-03 | 2011-03-03 | Method for improving metal leaching rate in waste lithium ion batteries by controlling oxidation-reduction potential |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102134642A true CN102134642A (en) | 2011-07-27 |
Family
ID=44294568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100504071A Pending CN102134642A (en) | 2011-03-03 | 2011-03-03 | Method for improving metal leaching rate in waste lithium ion batteries by controlling oxidation-reduction potential |
Country Status (1)
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|---|---|
| CN (1) | CN102134642A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703705A (en) * | 2012-05-28 | 2012-10-03 | 南昌航空大学 | Method for efficiently and intensively leaching metals in waste lithium ion batteries |
| CN103572048A (en) * | 2013-11-19 | 2014-02-12 | 东北大学 | Method of cobalt leaching with activated carbon catalysis bacteria |
| CN108808151A (en) * | 2018-06-14 | 2018-11-13 | 常熟理工学院 | A kind of method that separated in synchronization recycles cobalt, lithium, manganese in waste lithium ion cell anode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101174717A (en) * | 2007-11-22 | 2008-05-07 | 南昌航空大学 | Method for recovering valuable metals in waste lithium ion battery by bioleaching |
-
2011
- 2011-03-03 CN CN2011100504071A patent/CN102134642A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101174717A (en) * | 2007-11-22 | 2008-05-07 | 南昌航空大学 | Method for recovering valuable metals in waste lithium ion battery by bioleaching |
Non-Patent Citations (3)
| Title |
|---|
| 《Bioresource Technology》 20090804 Baoping Xin等 "Bioleaching mechanism of Co and Li from spent lithium-ion battery by the mixed culture of acidophilic sulfur-oxidizing and iron-oxidizing bacteria" 第6163-6169页 1 第100卷, * |
| 《南华大学学报》 20070331 李广悦等 "一株氧化亚铁硫杆菌菌株的筛选及其生长特性的研究" 第7-9、13页 1 第21卷, 第1期 * |
| 《甘肃冶金》 20040331 王玉棉等 "微生物浸矿的技术现状及展望" 第36-39页 1 第26卷, 第1期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703705A (en) * | 2012-05-28 | 2012-10-03 | 南昌航空大学 | Method for efficiently and intensively leaching metals in waste lithium ion batteries |
| CN103572048A (en) * | 2013-11-19 | 2014-02-12 | 东北大学 | Method of cobalt leaching with activated carbon catalysis bacteria |
| CN103572048B (en) * | 2013-11-19 | 2015-07-01 | 东北大学 | Method of cobalt leaching with activated carbon catalysis bacteria |
| CN108808151A (en) * | 2018-06-14 | 2018-11-13 | 常熟理工学院 | A kind of method that separated in synchronization recycles cobalt, lithium, manganese in waste lithium ion cell anode material |
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Application publication date: 20110727 |