CN112897580A - Method for preparing sodium ion battery cathode material antimony sulfide from high-arsenic antimony ash - Google Patents
Method for preparing sodium ion battery cathode material antimony sulfide from high-arsenic antimony ash Download PDFInfo
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- CN112897580A CN112897580A CN202110085741.4A CN202110085741A CN112897580A CN 112897580 A CN112897580 A CN 112897580A CN 202110085741 A CN202110085741 A CN 202110085741A CN 112897580 A CN112897580 A CN 112897580A
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- C—CHEMISTRY; METALLURGY
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- C01G30/008—Sulfides
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B30/02—Obtaining antimony
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
A method for preparing sodium ion battery cathode material antimony sulfide by using high-arsenic antimony soot. The invention uses high arsenic antimony ash (specific component is As)2O3、As4O6、Sb2O3Etc.) as raw material, arsenic is formed into soluble arsenate by adopting a pressure oxidation-alkaline leaching method and is filtered and removed; antimony (Sb) present in solid phase is then dissolved using dilute hydrochloric acid2O3) And obtaining a relatively pure antimony trichloride solution; under the condition of stirring, adding a proper amount of water-soluble sulfur source into the obtained solution and uniformly mixing; transferring the obtained mixed solution into a reaction kettle and carrying out hydrothermal reaction at a certain temperature; after the hydrothermal reaction is finished, washing the reaction product with alcohol for a plurality of times, and drying the reaction product to obtain the product. The patent avoids the lengthy metal extraction preparation process, and antimony is directly extractedThe antimony can be converted into sodium ion battery cathode materials with more practical value, and the recovery rate of antimony can reach more than 85%.
Description
Technical Field
The invention belongs to the field of preparation of a sodium ion battery cathode material by recycling high-arsenic antimony ash, and particularly relates to a sodium ion battery cathode material Sb2S3And a method of making the sameThe preparation method is as follows.
Background
Due to the progress and development of modern technology, the recovery technology of each valuable metal is mature, and the problems of complex ore components, low grade and the like can be effectively solved. In the common copper and lead smelting process, the common harmful impurity metal elements such as arsenic, antimony, bismuth and the like in the complex ore can be continuously circulated, enriched and accumulated in the processes of smelting, refining, electrolysis and the like, so that the smelting process of a target metal product becomes difficult. The method effectively controls and recovers part of impurity metal elements in the smelting process, can ensure normal smelting of target metal, and can achieve secondary utilization of other valuable metals. In the lead and copper smelting process, the ash with high arsenic and antimony is generated, and how to effectively recycle and efficiently utilize the secondary resources is a considerable problem.
The currently common recovery processes include roasting, leaching-precipitation, sodium sulfide-leaching-oxidation, acid leaching reduction-chlorination hydrolysis, chlorination, and the like. Specifically, CN105648227A is used for removing soluble arsenic in smoke dust through normal-pressure alkaline leaching, solid arsenic minerals are synthesized through an oxidation and growth regulation method, and leaching residues are subjected to washing, reduction smelting, oxidation blowing and other processes, so that valuable metal elements are recycled to the maximum extent; and for example, CN106834715A also adopts normal pressure alkaline leaching to transfer arsenic into the solution, then impurities such as antimony, lead, tin and the like in the leachate are separated out in a form of precipitation, the purified leachate is used for purifying zinc sulfate solution arsenic salt in zinc hydrometallurgy, and then the purified slag is sent to lead for smelting, so that separation and harmlessness of arsenic and valuable metals are realized; and finally, CN109777963A is used for separating lead and copper in the ash by high-temperature alkaline boiling, zinc, copper, tin, antimony, arsenic and the like are recovered by adopting methods such as precipitation, extraction, crystallization and the like, and finally, the separation of various valuable metals is achieved. However, in order to ensure the purity of the product, the above process inevitably loses part of the valuable metals during a lengthy recovery process. The method has the advantages that after the arsenic is removed, the ash is dissolved and directly used as an antimony source to prepare a suitable sodium ion battery cathode material, so that a long recovery process and flow-by-flow metal loss are avoided, secondary resource utilization of valuable metals is achieved, and a new direction is provided for recovery and reutilization of similar metallurgical wastes.
Disclosure of Invention
The invention provides a method for preparing antimony sulfide of a sodium ion battery cathode material by using high-arsenic antimony ash, which utilizes the high-arsenic antimony ash as a recovery object, adopts a pressure oxidation-alkaline leaching method to filter and remove arsenic, and filter residues are re-dissolved and then directly used as an antimony source to prepare a corresponding electrode material, so that the problem of a lengthy metal separation and extraction process is avoided, and meanwhile, antimony is efficiently recovered and regenerated into the sodium ion battery cathode material with excellent performance.
The invention adopts the following specific steps to solve the technical problem:
(1) and (4) removing arsenic. Converting arsenic in the soot into soluble arsenate by regulating and controlling proper oxygen pressure and under an alkaline leaching condition, and filtering the soluble arsenate once to obtain filtrate; the arsenic-containing alkali liquor can be returned to the alkali leaching process for recycling, calcium hydroxide is added to precipitate arsenic when the concentration of sodium arsenate is saturated, and the filtrate obtained after secondary filtration can still be returned to the alkali leaching process.
(2) And (3) preparing the material. The main component of the filter residue after primary filtration is antimony oxide, and an acid solution with a certain concentration is adopted to dissolve the antimony oxide to obtain a corresponding antimony salt solution; adding a water-soluble sulfur source into the obtained antimonate solution, uniformly mixing, transferring into a reaction kettle, and reacting at a high temperature for sufficient time to obtain a reaction product; and finally washing the product with alcohol for multiple times, and drying at a proper temperature.
Further, regulating and controlling the oxygen pressure in the step (1) to be 0.1-1 MPa;
further, one or more of sodium hydroxide, potassium hydroxide and ammonia water are required to be added in the alkaline leaching process in the step (1);
further, the pH value of the alkaline leaching condition in the step (1) is controlled to be 8-14.
Further, the acid solution for dissolving the primary filter residue in the step (2) adopts one or more of hydrochloric acid, sulfuric acid, nitric acid and oxalic acid;
further, controlling the pH value of the acid solution in the step (2) to be 1-6;
further, the sulfur source in the step (2) is selected from one or more of thiourea, thioacetamide, glutathione and sodium sulfide;
further, the molar ratio of sulfur in the sulfur source in the step (2) to antimony in the solution is 2: 1-6: 1;
further, the hydrothermal reaction temperature of the reaction kettle in the step (2) is 100-200 ℃;
further, the hydrothermal reaction time of the reaction kettle in the step (2) is 3-24 hours;
further, the drying temperature of the hydrothermal product in the step (2) is 50-120 ℃.
The invention has the beneficial effects that: the method has the advantages that after the arsenic is removed, the ash is dissolved and directly used as an antimony source to prepare a suitable sodium ion battery cathode material, so that a long recovery process and flow-by-flow metal loss are avoided, secondary resource utilization of valuable metals is achieved, and a new direction is provided for recovery and reutilization of similar metallurgical wastes.
Drawings
FIG. 1 shows a sodium-ion battery negative electrode material Sb prepared in example 1 of the present invention2S3XRD pattern of (a);
FIG. 2 shows the negative electrode material Sb of the sodium-ion battery prepared in example 1 of the invention2S3SEM picture of (1);
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
Adding 5g of high-arsenic antimony ash into an autoclave containing 50mL of 4mol/L NaOH solution, regulating oxygen pressure by blowing oxygen, and filtering to obtain filter residue after full reaction; after multiple water washing, 2mol/L H is adopted2SO4Dissolving the solution, and detecting specific ion concentration (As removal rate and Sb) by inductively coupled plasma spectrometer (ICP)3+Concentration in solution); according to the mol ratio of Sb to S being 1 to 2, adding thiourea into the solution, stirring uniformly and transferring to a high-pressure reaction kettle; controlling the hydrothermal temperature at 180 ℃ and the hydrothermal time at 80min, after the reaction is finished, washing the product with alcohol for many times, and drying at 80 ℃.
Weighing the above0.07g of prepared product, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, binder), fully grinding the mixture, adding a proper amount of NMP solution, uniformly mixing the slurry, pulling the slurry on a copper foil to prepare a sheet, drying the sheet at the temperature of 120 ℃ in vacuum, cutting the sheet into circular sheets with the diameter of 12mm, assembling the circular sheets in a glove box in the argon atmosphere, taking a metal sodium sheet as a counter electrode, and taking 1M NaClO4The solution (EC solvent: FEC with the DMC volume ratio of 1: 15%) is used as electrolyte, and glass fiber (Grade GF/F) is used as a diaphragm to assemble the CR2032 type button cell.
The product of this example was analyzed by X-ray powder diffraction and the results are shown in fig. 1.
The scanning electron microscope was used to scan the product of this example, and the results are shown in FIG. 2.
Example 2
Adding 5g of high-arsenic antimony ash into an autoclave containing 50mL of 5mol/L NaOH solution, regulating oxygen pressure by blowing oxygen, and filtering to obtain filter residue after full reaction; after multiple water washing, 3mol/L H is adopted2SO4Dissolving the solution, and detecting specific ion concentration (As removal rate and Sb) by inductively coupled plasma spectrometer (ICP)3+Concentration in solution); according to the mol ratio of Sb to S being 1 to 2.5, adding thiourea into the solution, stirring uniformly, and transferring into a high-pressure reaction kettle; controlling the hydrothermal temperature at 160 ℃ and the hydrothermal time at 100min, washing the product with alcohol for many times after the reaction is finished, and drying at 80 ℃.
Weighing 0.07g of the prepared product, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, binder), fully grinding, adding a proper amount of NMP solution, uniformly mixing, drawing slurry on a copper foil for flaking, drying at 120 ℃ in vacuum, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal sodium sheet as a counter electrode, and taking 1M NaClO4The solution (EC solvent: FEC with the DMC volume ratio of 1: 15%) is used as electrolyte, and glass fiber (Grade GF/F) is used as a diaphragm to assemble the CR2032 type button cell.
Example 3
5g of high arsenic antimony soot was added to an autoclave containing 50mL of 6mol/L NaOH solution,regulating oxygen pressure by blowing oxygen, and filtering to obtain filter residue after the reaction is full; after multiple water washing, 4mol/L H is adopted2SO4Dissolving the solution, and detecting specific ion concentration (As removal rate and Sb) by inductively coupled plasma spectrometer (ICP)3+Concentration in solution); according to the mol ratio of Sb to S being 1 to 3, thiourea is added into the solution, and the mixture is transferred into a high-pressure reaction kettle after being uniformly stirred; controlling the hydrothermal temperature at 140 ℃ and the hydrothermal time at 120min, after the reaction is finished, washing the product with alcohol for many times, and drying at 80 ℃.
Weighing 0.07g of the prepared product, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, binder), fully grinding, adding a proper amount of NMP solution, uniformly mixing, drawing slurry on a copper foil for flaking, drying at 120 ℃ in vacuum, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal sodium sheet as a counter electrode, and taking 1M NaClO4The solution (EC solvent: FEC with the DMC volume ratio of 1: 15%) is used as electrolyte, and glass fiber (Grade GF/F) is used as a diaphragm to assemble the CR2032 type button cell.
Claims (5)
1. A method for preparing sodium ion battery cathode material antimony sulfide by using high-arsenic antimony soot is characterized by comprising the following steps:
(1) and (4) removing arsenic. Converting arsenic in the soot into soluble arsenate by regulating and controlling proper oxygen pressure and under an alkaline leaching condition, and filtering the soluble arsenate once to obtain filtrate; the arsenic-containing alkali liquor can be returned to the alkali leaching process for recycling, calcium hydroxide is added to precipitate arsenic when the concentration of sodium arsenate is saturated, and the filtrate obtained after secondary filtration can still be returned to the alkali leaching process.
(2) And (3) preparing the material. The main component of the filter residue after primary filtration is antimony oxide, and an acid solution with a certain concentration is adopted to dissolve the antimony oxide to obtain a corresponding antimony salt solution; adding a water-soluble sulfur source into the obtained antimonate solution, uniformly mixing, transferring into a reaction kettle, and carrying out hydrothermal reaction at a high temperature for sufficient time to obtain a reaction product; and finally washing the product with alcohol for multiple times, and drying at a proper temperature.
The high-arsenic antimony soot comprises the following components: 20-60% of antimony, 20-40% of arsenic and other valuable metals such as lead, silver and the like.
2. The method for preparing antimony sulfide serving as a cathode material of a sodium-ion battery from high-arsenic antimony soot as claimed in claim 1, wherein the oxygen pressure in the step (1) is 0.1-1 MPa, one or more of sodium hydroxide, potassium hydroxide and ammonia water is/are added when the solution is alkaline, and the pH value of the alkaline leaching condition is controlled to be 8-14.
3. The method for preparing antimony sulfide serving as a sodium ion battery negative electrode material from high-arsenic antimony soot as claimed in claim 1, wherein one or more of hydrochloric acid, sulfuric acid, nitric acid and oxalic acid are adopted as the acid solution for dissolving the primary filter residue in the step (2), and the pH of the acid solution is controlled to be 1-6.
4. The method for preparing antimony sulfide serving as a sodium ion battery negative electrode material from high-arsenic antimony soot as claimed in claim 1, wherein the sulfur source in the step (2) is selected from one or more of thiourea, thioacetamide, glutathione and sodium sulfide, and the molar ratio of sulfur in the sulfur source to antimony in the solution is 2: 1-6: 1.
5. The method for preparing antimony sulfide serving as a negative electrode material of a sodium-ion battery from high-arsenic antimony soot as claimed in claim 1, wherein in the step (2), the hydrothermal reaction temperature of the reaction kettle is 100-200 ℃, the hydrothermal reaction time is 3-24 hours, and the drying temperature is 50-120 ℃.
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| CN202110085741.4A CN112897580A (en) | 2021-01-22 | 2021-01-22 | Method for preparing sodium ion battery cathode material antimony sulfide from high-arsenic antimony ash |
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| CN202110085741.4A CN112897580A (en) | 2021-01-22 | 2021-01-22 | Method for preparing sodium ion battery cathode material antimony sulfide from high-arsenic antimony ash |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875244A (en) * | 2022-05-11 | 2022-08-09 | 中南大学 | Method for recycling high-arsenic antimony smelting soot |
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2021
- 2021-01-22 CN CN202110085741.4A patent/CN112897580A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| LOVE DASHAIRYA ET AL.: ""Antimony Sulphide Nanorods Decorated onto Reduced Graphene Oxide Based Anodes for Sodium-Ion Battery"，", 《MATERIALS TODAY: PROCEEDINGS》 * |
| 张旭等: ""苛性碱溶液氧压浸出高砷锑烟尘"", 《中南大学学报(自然科学版)》 * |
| 石得中等: "《世界精细化工产品技术经济手册》", 31 December 1988, 化学工业部科学技术情报研究所出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875244A (en) * | 2022-05-11 | 2022-08-09 | 中南大学 | Method for recycling high-arsenic antimony smelting soot |
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Application publication date: 20210604 |