CN112531227A - Harmless recycling method for electrolyte in waste lithium ion battery - Google Patents
Harmless recycling method for electrolyte in waste lithium ion battery Download PDFInfo
- Publication number
- CN112531227A CN112531227A CN201910746383.XA CN201910746383A CN112531227A CN 112531227 A CN112531227 A CN 112531227A CN 201910746383 A CN201910746383 A CN 201910746383A CN 112531227 A CN112531227 A CN 112531227A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lime milk
- water
- phase
- density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- 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
Abstract
A method for reclaiming the electrolyte from waste Li-ion battery includes such steps as cutting the fully discharged battery, and immersing it in the lime milk solution prepared in advance and containing water-soluble colour pigment. Mixing organic part of electrolyte, fluorine-containing electrolyte and Ca (OH) in lime milk2Fully reacting to generate inorganic mineral substances and an organic phase. Due to the difference of the density of the organic solvent and water in the electrolyte, the layering phenomenon can occur after standing. And because the colored dye is added into the lime milk aqueous solution, the visual effect of layering is very obvious. Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be finally obtained. Compared with the prior art, the invention has green and pollution-free recovery treatment process, and the inventionThe valuable components in the process are effectively utilized, the additional value of the recovery is improved, the cost is low, and the efficiency is high.
Description
Technical Field
The invention belongs to the field of waste lithium ion battery recovery, and particularly relates to a recovery processing method of electrolyte in a waste lithium ion battery.
Background
In recent years, with the rise of the electric automobile industry and the field of large-scale energy storage, the production and sales volume of lithium ion batteries in China are increased year by year. In 2017, the yield of Chinese lithium batteries breaks through 100 hundred million, in 2018, the yield of national lithium batteries reaches 121 hundred million, and the domestic lithium ion battery industry enters a rapid growth stage and becomes a main world of lithium ion battery producing countries and consuming countries. A large number of lithium ion batteries face the problem of disposal after 3-5 years of use. Although large-scale recycling enterprises are gradually appearing in China, the enterprises mainly focus on recycling electrode materials, and an effective green and environment-friendly treatment means is not available for treating the electrolyte.
In the collecting, stacking and recycling processes of the waste lithium ion batteries, part of electrolyte is leaked and volatilized, and the surrounding atmospheric soil and water can be polluted. Lithium ion battery electrolytes are mainly composed of two major classes: an organic solvent and an electrolytic lithium salt. The organic solvents are widely used as ethers and carbonates, such as Dimethoxyethane (DME), Propylene Carbonate (PC), Ethylene Carbonate (EC), and diethyl carbonate (DEC). Electrolyte lithium salts, e.g. lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) And lithium hexafluorophosphate (LiPF)6). In addition, the electrolyte also contains a small amount of additives, which mainly can improve the performance of a Solid Electrolyte Interface (SEI) film, the low-temperature performance, the thermal stability, the safety, the cycling stability, the conductivity and the like of the electrolyte, such as Vinylene Carbonate (VC), Ethyl Acetate (EA) and Biphenyl (BP).
The organic solvent is subjected to chemical reactions such as hydrolysis combustion and decomposition to generate micromolecular organic matters such as formaldehyde, methanol, acetaldehyde, ethanol, formic acid and the like. These substances are easily dissolved in water, and can cause water source pollution and personal injury. When the electrolyte lithium salt enters the environment, chemical reactions such as hydrolysis, oxidation and the like can occur, and fluorine-containing arsenic-containing and phosphorus-containing compounds are generated, so that fluorine pollution, arsenic pollution and phosphorus pollution are caused.
The recovery technology of lithium ion batteries can be divided into a pyrogenic process and a wet process. In the pyrogenic process treatment technology, great potential safety hazards can be brought to production, and serious environmental pollution can be caused. The electrolyte organic solvent is volatilized or burnt to decompose into water and carbon dioxide gas to be discharged, and electrolyte lithium salt forms fluorine-containing smoke and dust to be discharged outwards, so that the environmental pollution is aggravated. The wet treatment process can be subdivided into methods of organic solvent soaking, organic solvent extraction, acid-base leaching and the like. The principle of the organic solvent soaking method is to separate an active material from a current collector by dissolving a binder (PVDF or PTFE) using a suitable organic solvent. More effective organic solvents include N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO). In the organic solvent extraction, an organic solvent or a supercritical fluid is used as an extracting agent, so that the extraction efficiency is considered, the organic solvent is easy to separate from an extracted substance, or new impurities are introduced in the process of recovering the electrolyte, the recovery cost of the waste lithium ion battery is increased, and new pollution is brought to the environment. The main principle of acid-base leaching is that an acid solution is used for dissolving positive active substances or an alkali solution is used for dissolving a positive current collector aluminum foil, so that the effect of separating the active substances from the current collector is achieved. However, the electrolyte is easy to form soluble fluoride with alkali liquor, so that fluorine pollution of a water body is caused, and certain harm is brought to the recovery operation of the battery. Once the fluorine-containing waste water and waste residues are dissolved and permeated into soil, the pollution of soil and water is directly caused, and fluorine-containing dust and waste gas are finally brought back to the ground surface by rainwater to cause pollution. Therefore, the treatment of the electrolyte of the waste lithium ion battery by a proper method is not only a guarantee on production safety and protection of natural environment, but also a necessary condition for smooth production of lithium ion battery recycling enterprises.
The invention cuts the fully discharged lithium ion battery and then soaks the lithium ion battery in lime cream (Ca (OH)2In the suspension, the electrolyte is mixed with Ca (OH)2The solution is fully reacted, and meanwhile, the fluorine-containing electrolyte LiPF in the electrolyte6Hydrolysis reactions also occur, as shown by the following equation:
LiPF6+Ca(OH)2→CaF2+Ca3(PO4)2+LiOH+H2O；
disclosure of Invention
The invention aims to develop a novel method for recovering and treating the electrolyte in the waste lithium ion battery, which is simple to operate, efficient, environment-friendly, low in cost and suitable for industrial production.
The technical scheme of the invention is as follows:
a harmless recycling method of electrolyte in waste lithium ion batteries comprises the following steps:
(1) firstly, completely discharging the battery until the voltage is zero;
(2) cutting the position of a battery cover plate (or a lug) by a mechanical cutting method;
(3) preparing lime milk solution, and simultaneously adding water-soluble blue, red, orange or other colored dyes into the lime milk solution;
(4) soaking the cut battery in lime milk solution added with pigment to fully soak the battery cell in the lime milk solution, wherein in the process, the organic part of electrolyte, fluorine-containing electrolyte and Ca (OH) in the lime milk2Fully reacting;
(5) standing for 5-50h, wherein the density of the organic solvent in the electrolyte is different from that of water, so that the layering phenomenon can occur after standing; the lime milk used for many times is divided into four layers after standing, and the layering visual effect is very obvious because colored dye is added into the lime milk aqueous solution; the effect after the liquid separation is shown in figure 1.
(6) Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be obtained.
The invention has the advantages that: compared with the prior art, the invention has the following beneficial effects: (1) after the organic components in the electrolyte are classified and recovered, the organic components can be delivered to an electrolyte manufacturer or an organic solvent manufacturer for further treatment, so that the valuable components in the electrolyte are effectively utilized, the pollution to the environment can be reduced, and the additional value of the recovery is also improved; (2) the electrolyte is recovered by utilizing the simple principle (according to different DMC, DEC, EMC, EC density and water solubility), so that the cost is lowMoreover, the efficiency is high; (3) the electrolyte is recovered through a static layering process, and the method is environment-friendly and easy for industrial implementation. (4) The recovery process is simple and efficient, the energy is saved, and (5) the solid residue phase obtained in the recovery process is CaF2(commonly known as fluorite), Ca3(PO4)2(mineral can also be used as phosphate fertilizer), thereby realizing the green recovery concept from the mine to the mine.
Drawings
FIG. 1 is a schematic diagram of the liquid stratification effect of step (5) in the context of the present invention.
Detailed Description
The invention provides a harmless recycling method of electrolyte in waste lithium ion batteries, and a specific implementation method is further explained below to better understand the invention.
Example 1:
a harmless recycling treatment mode of electrolyte in waste lithium ion batteries comprises the following steps:
(1) firstly, completely discharging the battery until the voltage is zero;
(2) cutting the position of a battery cover plate (or a lug) by a mechanical cutting method;
(3) preparing a lime milk solution, and simultaneously adding a water-soluble blue pigment into the lime milk solution;
(4) soaking the cut battery in lime milk solution added with pigment to fully soak the battery cell in the lime milk solution, wherein in the process, the organic part of electrolyte, fluorine-containing electrolyte and Ca (OH) in the lime milk2Fully reacting;
(5) standing for 5h, wherein the density of an organic solvent in the electrolyte is different from that of water, so that a layering phenomenon can occur after standing; the lime milk used for many times is divided into four layers after standing, and the blue dye is added into the lime milk aqueous solution, so that the layering visual effect is very obvious.
(6) Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be obtained.
Example 2:
a harmless recycling treatment mode of electrolyte in waste lithium ion batteries comprises the following steps:
(1) firstly, completely discharging the battery until the voltage is zero;
(2) cutting the position of a battery cover plate (or a lug) by a mechanical cutting method;
(3) preparing a lime milk solution, and simultaneously adding a water-soluble red pigment into the lime milk solution;
(4) soaking the cut battery in lime milk solution added with pigment to fully soak the battery cell in the lime milk solution, wherein in the process, the organic part of electrolyte, fluorine-containing electrolyte and Ca (OH) in the lime milk2Fully reacting;
(5) standing for 50h, wherein the density of an organic solvent in the electrolyte is different from that of water, so that a layering phenomenon can occur after standing; the lime milk used for many times is divided into four layers after standing, and the layering visual effect is very obvious because red dye is added into the lime milk aqueous solution.
(6) Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be obtained.
Example 3:
a harmless recycling treatment mode of electrolyte in waste lithium ion batteries comprises the following steps:
(1) firstly, completely discharging the battery until the voltage is zero;
(2) cutting the position of a battery cover plate (or a lug) by a mechanical cutting method;
(3) preparing a lime milk solution, and simultaneously adding a water-soluble orange pigment into the lime milk solution;
(4) soaking the cut battery in lime milk solution added with pigment to fully soak the battery cell in the lime milk solution, wherein in the process, the organic part of electrolyte, fluorine-containing electrolyte and Ca (OH) in the lime milk2Fully reacting;
(5) standing for 20h, wherein the density of an organic solvent in the electrolyte is different from that of water, so that a layering phenomenon can occur after standing; the lime milk used for many times can be divided into four layers after standing, and the orange pigment is added into the lime milk aqueous solution, so that the layering visual effect is very obvious.
(6) Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be obtained.
Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be obtained.
Claims (3)
1. A harmless recycling method of electrolyte in waste lithium ion batteries comprises the following steps:
(1) firstly, completely discharging the battery until the voltage is zero;
(2) cutting the position of a battery cover plate (or a lug) by a mechanical cutting method;
(3) preparing a lime milk solution, and simultaneously adding a water-soluble colored pigment into the lime milk solution;
(4) soaking the cut battery in lime milk solution added with pigment to fully soak the battery cell in the lime milk solution, wherein in the process, the organic part of electrolyte, fluorine-containing electrolyte and Ca (OH) in the lime milk2Fully reacting;
(5) standing for 5-50h, wherein the density of the organic solvent in the electrolyte is different from that of water, so that the layering phenomenon can occur after standing; the lime milk used for many times can be divided into four layers after standing, and the layering visual effect is very obvious because the color pigment is added into the lime milk aqueous solution.
(6) Through liquid separation, four parts of an organic phase with density less than that of water, an aqueous solution phase, an organic phase with density more than that of water and a solid residue phase can be obtained.
2. In step 3) of claim 1, the water-soluble colored pigment is a vivid color, preferably red, blue, orange, etc.
3. In the step 5) of claim 1, the harmless recycling method of the electrolyte in the waste lithium ion battery, which obtains the target product by distillation, is characterized in that: no additional reactant, directly obtaining the target product in one step, saving energy, and being simple and easy for industrialized implementation. The recovery process realizes the green recovery concept of 'from mine to mine'.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910746383.XA CN112531227A (en) | 2019-09-17 | 2019-09-17 | Harmless recycling method for electrolyte in waste lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910746383.XA CN112531227A (en) | 2019-09-17 | 2019-09-17 | Harmless recycling method for electrolyte in waste lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112531227A true CN112531227A (en) | 2021-03-19 |
Family
ID=74973923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910746383.XA Pending CN112531227A (en) | 2019-09-17 | 2019-09-17 | Harmless recycling method for electrolyte in waste lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112531227A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023231508A1 (en) * | 2022-05-31 | 2023-12-07 | 广东邦普循环科技有限公司 | Method for efficiently recovering electrolyte of spent lithium-ion battery |
-
2019
- 2019-09-17 CN CN201910746383.XA patent/CN112531227A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023231508A1 (en) * | 2022-05-31 | 2023-12-07 | 广东邦普循环科技有限公司 | Method for efficiently recovering electrolyte of spent lithium-ion battery |
| GB2622974A (en) * | 2022-05-31 | 2024-04-03 | Guangdong Brunp Recycling Technology Co Ltd | Method for efficiently recovering electrolyte of spent lithium-ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108288738B (en) | Method for recovering lithium ion battery electrolyte by using supercritical carbon dioxide fluid | |
| CN105406146B (en) | The carbon dioxide sub critical extraction and recovery reuse method of waste and old lithium ionic cell electrolyte | |
| CN105932351A (en) | Resource recycling method for waste lithium batteries | |
| US7198865B2 (en) | System and method for removing an electrolyte from an energy storage and/or conversion device using a supercritical fluid | |
| CN110203949B (en) | Method for fully recycling electrolyte of waste lithium ion battery | |
| CN102496752B (en) | Method for recycling electrolyte of waste lithium ion battery | |
| CN108281729A (en) | A kind of waste and old lithium ionic cell electrolyte recovery process | |
| CN103825064A (en) | Demonstration process for recovering waste and old dynamic lithium iron phosphate cell in environmental protection mode | |
| CN106654437B (en) | Method for recovering lithium from lithium-containing battery | |
| CN104852102A (en) | Method and device for recycling and harmlessly treating waste lithium ion battery electrolyte | |
| CN108565519A (en) | A kind of waste lithium cell electrolyte recycling processing method | |
| CN105390765A (en) | Recovery method for electrolyte solution of lithium ion battery | |
| CN106252777A (en) | A kind of recovery method of lithium-ion battery electrolytes | |
| CN204577540U (en) | A kind of recycle device of waste and old lithium ionic cell electrolyte | |
| WO2023155543A1 (en) | Method for recycling electrolyte of lithium-ion battery | |
| CN103951689A (en) | Preparation method of liquid lithium bisoxalate borate | |
| CN112531227A (en) | Harmless recycling method for electrolyte in waste lithium ion battery | |
| CN114759286A (en) | Method for recovering waste electrolyte of lithium ion battery | |
| JP2018022670A (en) | Method for removing electrolyte anionic moieties of used lithium ion battery | |
| WO2024021232A1 (en) | Method for underwater crushing and electrolyte solution recycling of waste lithium ion battery | |
| CN112397803B (en) | Method for recovering anode material from lithium battery anode | |
| CN109672002B (en) | Method for efficiently removing lithium hexafluorophosphate in battery cell powder | |
| CN116675236A (en) | LiPF (LiPF) treatment by high-frequency electromagnetic waves 6 Method for preparing condensed electrolyte and by-product high-purity lithium chloride | |
| CN116675234A (en) | LiBF (LiBF) treated by high-frequency electromagnetic waves 4 Method for preparing condensed electrolyte and by-producing lithium chloride and sodium borate | |
| Mao et al. | Recycling of electrolyte from spent lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210319 |
|
| WD01 | Invention patent application deemed withdrawn after publication |