CN110224115B - Lithium ion battery cathode material and preparation method and application thereof - Google Patents
Lithium ion battery cathode material and preparation method and application thereof Download PDFInfo
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- CN110224115B CN110224115B CN201810175305.4A CN201810175305A CN110224115B CN 110224115 B CN110224115 B CN 110224115B CN 201810175305 A CN201810175305 A CN 201810175305A CN 110224115 B CN110224115 B CN 110224115B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 239000010406 cathode material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000009713 electroplating Methods 0.000 claims abstract description 64
- 239000010802 sludge Substances 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 235000021110 pickles Nutrition 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 29
- 244000063299 Bacillus subtilis Species 0.000 claims description 27
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 27
- 238000002386 leaching Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000011081 inoculation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 9
- 239000011135 tin Substances 0.000 abstract description 35
- 241000894006 Bacteria Species 0.000 abstract description 16
- 229910052718 tin Inorganic materials 0.000 abstract description 16
- 238000007599 discharging Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- -1 iron ions Chemical class 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000011366 tin-based material Substances 0.000 abstract description 2
- 239000001963 growth medium Substances 0.000 description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 229910020900 Sn-Fe Inorganic materials 0.000 description 8
- 229910019314 Sn—Fe Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229940041514 candida albicans extract Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000012137 tryptone Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012138 yeast extract Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000003321 amplification Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Images
Classifications
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 provides a lithium ion battery cathode material and a preparation method and application thereof. According to the invention, bacteria are added into the pickle liquor to absorb tin and iron ions, a composite material precursor is obtained through stirring and filtering, and then the precursor is calcined in an inert gas atmosphere to obtain the Sn/Fe @ C lithium ion battery composite negative electrode material, so that the preparation process is simple, easy to operate and easy to control; can not only complete the recycling of the electroplating sludge, but also solve the problem of the swelling of the tin-based material, thereby realizing the technical route of high-value utilization of the wastes. The lithium ion battery cathode material can well relieve the volume change of metal tin in the charging and discharging processes, avoids the volume expansion of tin in the charging and discharging processes, and has excellent cycle stability and higher capacity; when the composite material is used as a lithium battery negative electrode material, the composite material shows good electrochemical performance and can better meet the requirements of the current market.
Description
Technical Field
The invention relates to a method for recovering and extracting metals from electroplating sludge, in particular to a lithium ion battery cathode material and a preparation method and application thereof.
Background
With the rapid development of the electroplating industry, the amount of electroplating sludge is also rapidly increasing. The electroplating sludge contains a large amount of metals (tin, iron, copper, chromium, nickel, zinc, etc.). If the electroplating sludge is not properly treated, the method can cause fatal threats to the physical health and the ecological environment of human beings. Therefore, the harmless treatment of the electroplating sludge and the high-value recovery of heavy metals in the electroplating sludge become the popular research direction in the industry.
At present, the following methods are mainly used for treating the electroplating sludge:
1. the sludge is directly buried after dehydration.
2. And (4) carrying out pyrometallurgical treatment.
3. Ion exchange membrane process.
4. Ammonia leaching method.
5. Acid leaching method.
6. Biological method.
However, because the electroplating sludge contains a large amount of undegradable heavy metals, the above treatment method has great disadvantages and risks, such as: high treatment cost, easy generation of secondary environmental pollution and the like.
The electroplating sludge contains a large amount of metal elements such as tin, iron, copper and the like. Wherein, the tin has high theoretical capacity of 994mAh/g, and is a lithium ion battery cathode material with a far-reaching application prospect. It has the advantages of low de-intercalation platform, high theoretical capacity of battery, etc. However, tin is likely to undergo volume expansion during charging and discharging, and electrode materials are pulverized and dropped, resulting in a decrease in battery capacity and deterioration in cycle performance, so that it is difficult to realize commercial production and application.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing a lithium ion battery cathode material by using electroplating sludge. The characteristic that bacteria selectively absorb heavy metal is utilized to treat heavy metal ions in the electroplating sludge pickle liquor. Adding bacteria into the pickle liquor to absorb tin and iron ions, stirring and carrying out vacuum filtration to obtain a composite material precursor, and calcining the precursor in an inert gas atmosphere to obtain the Sn/Fe @ C lithium ion battery composite negative electrode material. And (3) selectively extracting and recovering tin in the electroplating sludge by using the bacillus subtilis as a carrier to prepare the high-performance lithium ion battery cathode material. Can not only complete the recycling of the electroplating sludge, but also solve the problem of the swelling of the tin-based material, thereby realizing the technical route of high-value utilization of the wastes.
The invention also aims to provide the lithium ion battery negative electrode material prepared by the method. The metal ion battery negative electrode composite material avoids volume expansion of tin in the charging and discharging processes, and shows good electrochemical performance when the composite material is used as a lithium battery negative electrode material.
The invention further aims to provide the method or the application of the lithium ion battery negative electrode material.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a lithium ion battery cathode material by using electroplating sludge comprises the following preparation steps:
(1) adding inorganic acid into the electroplating sludge, uniformly stirring, and filtering to obtain electroplating sludge pickle liquor containing tin and iron;
(2) inoculating bacillus subtilis into the culture solution, and culturing to obtain a bacillus subtilis solution;
(3) adding the acid leaching solution of the electroplating sludge obtained in the step (1) into the bacillus subtilis liquid obtained in the step (2), and uniformly mixing to obtain a mixed solution;
(4) filtering the mixed solution obtained in the step (3), and drying to obtain a precursor of the bacillus subtilis and tin-iron composite material;
(5) and (2) calcining the precursor of the composite material of the bacillus subtilis and the tin iron at high temperature in an inert or reducing atmosphere to obtain the Sn/Fe @ C composite material.
The pH value of the pickle liquor in the step (1) is preferably 4-8.
The inorganic acid in the step (1) is preferably one or at least two of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
The concentration of the inorganic acid in the step (1) is preferably 0.1-3 mol/L.
The stirring time in the step (1) is preferably 1-3 h.
The inoculation amount of the bacillus subtilis in the step (2) is preferably 1-10%.
The culture solution in step (2) is preferably prepared by the following method: dissolving 10g tryptone, 5g yeast extract and 5g sodium chloride in 1L deionized water, and stirring.
The culture time in the step (2) is preferably 12-24 h.
The mixing in step (3) is preferably carried out by shaking or stirring; the mixing time is preferably 1-24 h.
The bacillus subtilis liquid and the electroplating sludge acid leaching liquid in the step (3) are preferably mixed according to the volume ratio of 1: (0.1-5); further preferably, the amount of the water-soluble polymer is 1: (1-3) mixing.
The filtration in the step (4) is preferably one or at least two of gravity filtration, centrifugal filtration and vacuum filtration.
The drying in the step (4) is preferably one or at least two of atmospheric drying, vacuum drying and freeze drying.
The inert or reducing atmosphere in the step (5) is preferably one or a mixture of at least two of nitrogen, argon and hydrogen.
The high-temperature calcination in the step (5) is preferably performed by heating to 500-900 ℃ at a heating rate of 1-15 ℃/min for 1-10 h.
The lithium ion battery cathode material prepared by the method.
The preparation method or the application of the lithium ion battery negative electrode material in the field of lithium ion batteries.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention utilizes the electroplating sludge of industrial waste in a high-value way, uses the microorganism as the processing material, and has wide source and low cost. Can realize the purpose of high-value utilization of waste and solve the environmental problem. The research utilizes the electroplating sludge in a high-value manner, provides a new idea for harmless treatment of the electroplating sludge and also provides a new idea for preparing electrochemical energy storage materials.
(2) The preparation process is simple, easy to operate and easy to control.
(3) The bacteria in the composite material prepared by the invention are partially graphene-based after high-temperature calcination, which is beneficial to ion and electron transmission.
(4) In the Sn/Fe @ C composite material prepared by the invention, the volume change of the metallic tin in the charging and discharging process can be well relieved by using bacteria as a carrier of the metallic tin iron, and the obtained material has superior performanceHas a high capacity at a current density of 1A g-1The specific capacity can reach 620.4mAh g-1And the specific capacity retention rate is more than 95% after 1000 cycles. Compared with other methods for preparing electrode materials, such as the technical schemes described in patent documents with application numbers of CN201310715142.1 and CN200910193554.7, the method of the invention has superior cycling stability and high specific capacity, and can better meet the requirements of the current market.
Drawings
FIG. 1 is an XRD spectrum of the Sn-Fe @ C composite material prepared in example 1.
FIG. 2 is an SEM image of the Sn-Fe @ C composite material prepared in example 1.
FIG. 3 is a graph showing the first charge and discharge curves at a current density of 0.1A/g for a button cell assembled from the Sn-Fe @ C composite material prepared in example 2.
FIG. 4 is an SEM image of the Sn-Fe @ C composite material prepared in example 2.
FIG. 5 is a graph of the cycling performance of a button cell assembled from the Sn-Fe @ C composite material prepared in example 3 at a current density of 1A/g.
FIG. 6 is a graph of rate performance of button cells assembled from the Sn-Fe @ C composite material prepared in example 3 at different current densities.
FIG. 7 is an XRD pattern of the Sn-Fe @ C composite material prepared in example 4.
FIG. 8 is an SEM image of the Sn-Fe @ C composite material prepared in example 4.
FIG. 9 is an SEM photograph of a composite material obtained in comparative example 2.
FIG. 10 is a graph of the cycling performance of the button cell made of the composite material prepared in comparative example 2 at a current density of 1A/g.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Preparing a culture medium: weighing 10g of tryptone, 5g of yeast extract and 5g of sodium chloride, dissolving in 1L of deionized water, and uniformly stirring to form a stable clear solution.
(2) Electroplating sludge acid leaching solution: the electroplating sludge is placed in an oven, dried for 12 hours at 90 ℃, ground and sieved by a two-hundred-mesh sieve. Taking 10g of dried electroplating sludge, adding 50mL of 1mol/L hydrochloric acid, stirring for 2h, and filtering to obtain filtrate which is electroplating sludge pickle liquor with pH of 5.4.
(3) Inoculating bacteria: inoculating a Bacillus subtilis ATCC-6633 strain to the culture medium prepared in the step (1) with the inoculation amount of 1%, and placing the culture medium in a constant-temperature shaking table for activation for 12 hours;
(4) and (3) amplification culture: inoculating the activated bacillus subtilis in the step (3) on the culture medium prepared in the step (1) by using the inoculation amount of 1%, and placing the culture medium in a constant-temperature shaking table for culturing for 12 hours to obtain a bacillus subtilis liquid;
(5) adding the electroplating sludge acid leaching solution obtained in the step (2) into the bacterial culture medium subjected to the enlarged culture in the step (4), wherein the volume ratio of the acid leaching solution to the culture medium is 1: 1, stirring for 6 hours;
(6) carrying out suction filtration on the solution to obtain a composite material precursor;
(7) and drying the composite material precursor, calcining for 2h at 600 ℃ in an argon atmosphere (the heating rate is 10 ℃/min), and cooling to obtain the Sn/Fe @ C composite material.
The physical and chemical properties of the prepared Sn/bacteria composite material are characterized as shown in figures 1 and 2, wherein figure 1 is an XRD (X-ray diffraction) pattern of the prepared Sn/Fe @ C composite material, and figure 2 is an SEM (scanning Electron microscope) pattern of the Sn/Fe @ C composite material prepared in example 1.
XRD shows that simple substance tin and iron-tin alloy exist in the Sn/Fe @ C composite material prepared in the embodiment, and SEM shows that the composite material is good in appearance, and tin and iron-tin alloy are uniformly distributed on the surface of bacteria.
The obtained product is assembled into a button cell to test the discharge capacity of the button cell, and charge and discharge are carried out within the range of 0.01-2.5V. FIG. 3 shows the first charge/discharge curve at a current density of 0.1A/g. Meanwhile, the capacity of the composite material reaches 898.2 mAh/g.
Example 2
(1) Preparing a culture medium: weighing 10g of tryptone, 5g of yeast extract and 5g of sodium chloride, dissolving in 1L of deionized water, and uniformly stirring to form a stable clear solution.
(2) Electroplating sludge acid leaching solution: the electroplating sludge is placed in an oven, dried for 12 hours at 90 ℃, ground and sieved by a two-hundred-mesh sieve. Taking 10g of dried electroplating sludge, adding 50mL of 0.1mol/L nitric acid, stirring for 3h, and filtering to obtain filtrate, namely electroplating sludge pickle liquor, wherein the pH value is 6.8.
(3) Inoculating bacteria: inoculating Bacillus subtilis ATCC-6633 to the culture medium prepared in the step (1) with the inoculation amount of 1%, and placing the culture medium in a constant-temperature shaking table for activation for 12 hours;
(4) and (3) amplification culture: inoculating the activated bacteria obtained in the step (3) on the culture medium prepared in the step (1) by an inoculation amount of 5%, and placing the culture medium in a constant-temperature shaking table for culturing for 24 hours to obtain a bacillus subtilis liquid;
(5) adding the acid leaching solution of the electroplating sludge obtained in the step (2) into the bacillus subtilis liquid obtained in the step (4), wherein the volume ratio of the acid leaching solution to the culture medium is 2: 1, stirring for 12 hours;
(6) carrying out suction filtration on the solution to obtain a composite material precursor;
(7) and drying the composite material precursor, calcining for 2h at 700 ℃ in a nitrogen atmosphere (the heating rate is 7 ℃/min), and cooling to obtain the Sn/Fe @ C composite material.
The physical and chemical properties of the prepared Sn/Fe @ C composite material are shown in figures 4 and 5, figure 4 is an SEM image of the prepared Sn/Fe @ C composite material, and figure 4 shows that tin and tin-iron alloy are uniformly distributed on the surface of bacteria. The obtained Sn/Fe @ C composite material is assembled into a button cell, a circulation performance diagram under the current density of 1A/g is shown in figure 5, the first specific capacity under the multiplying power reaches 620.4mAh/g, and the specific capacity retention rate is more than 95% after 1000 times of circulation.
Example 3
1) Preparing a culture medium: weighing 10g of tryptone, 5g of yeast extract and 5g of sodium chloride, dissolving in 1L of deionized water, and uniformly stirring to form a stable clear solution.
(2) Electroplating sludge acid leaching solution: the electroplating sludge is placed in an oven, dried for 12 hours at 90 ℃, ground and sieved by a two-hundred-mesh sieve. Taking 10g of dried electroplating sludge, adding 50mL of 2mol/L hydrochloric acid, stirring for 2h, and filtering to obtain filtrate, namely electroplating sludge pickle liquor, wherein the pH value is 8.0.
(3) Inoculating bacteria: inoculating Bacillus subtilis ATCC-6633 to the culture medium prepared in the step (1) with the inoculation amount of 1%, and placing the culture medium in a constant-temperature shaking table for activation for 12 hours;
(4) and (3) amplification culture: inoculating the activated bacteria in the step (3) on the culture medium prepared in the step (1) by 10 percent of inoculation amount, and placing the culture medium in a constant-temperature shaking table for culturing for 24 hours;
(5) adding the acid leaching solution of the electroplating sludge obtained in the step (2) into the bacterial culture medium subjected to the enlarged culture in the step (4), wherein the volume ratio of the acid leaching solution of the electroplating sludge to the culture medium is 3: 1, stirring for 24 hours;
(6) carrying out suction filtration on the solution to obtain a composite material precursor;
(7) and drying the composite material precursor, calcining at 500 ℃ for 2h (the heating rate is 5 ℃/min) in a nitrogen-hydrogen mixed atmosphere (95% of nitrogen and 5% of hydrogen), and cooling to obtain the Sn/Fe @ C composite material.
And assembling the Sn/Fe @ C composite material into a button cell to test the charge-discharge capacity of the button cell, and carrying out cycle life test within the range of 0.01-2.5V. As shown in fig. 6, the rate capability of the button cell is shown under different current densities, and it can be seen that the Sn/Fe @ C composite material has excellent rate capability.
Comparative example 1
(1) Preparing a culture medium: weighing 10g of tryptone, 5g of yeast extract and 5g of sodium chloride, dissolving in 1L of deionized water, and uniformly stirring to form a stable clear solution.
(2) Electroplating sludge acid leaching solution: the electroplating sludge is placed in an oven, dried for 12 hours at 90 ℃, ground and sieved by a two-hundred-mesh sieve. Taking 10g of dried electroplating sludge, adding 50mL of 2mol/L nitric acid, stirring for 2h, and filtering to obtain filtrate, namely electroplating sludge pickle liquor, wherein the pH value is 5.4.
(3) Inoculating bacteria: inoculating Bacillus subtilis ATCC-6633 to the culture medium prepared in the step (1) with an inoculation amount of 5%, and placing the culture medium in a constant-temperature shaking table for activation for 12 hours;
(4) and (3) amplification culture: inoculating the activated bacillus subtilis in the step (3) on the culture medium prepared in the step (1) by 10% of inoculation amount, and placing the culture medium in a constant-temperature shaking table for culturing for 24 hours to obtain bacillus subtilis liquid;
(5) adding the acid leaching solution of the electroplating sludge obtained in the step (2) into the bacillus subtilis liquid obtained in the step (4), wherein the volume ratio of the acid leaching solution of the electroplating sludge to the culture medium is 3: 1, stirring for 12 hours;
(6) carrying out suction filtration on the solution to obtain a composite material precursor;
(7) and drying the composite material precursor, calcining at 900 ℃ for 5h (the heating rate is 1 ℃/min) in a nitrogen-argon mixed atmosphere, and cooling to obtain the Sn/Fe @ C composite material.
An XRD (X-ray diffraction) spectrum of the obtained Sn/Fe @ C composite material is shown in figure 7, and the existence form of tin in the composite material is proved to be metal simple substance tin through PDF card retrieval. However, as can be seen from the SEM result of fig. 8, the original morphology of the bacteria is not maintained in the composite material, and the morphology of the rod-shaped bacteria is destroyed, which has a great influence on the electrochemical performance of the composite material.
Comparative example 2
(1) Electroplating sludge acid leaching solution: the electroplating sludge is placed in an oven, dried for 12 hours at 90 ℃, ground and sieved by a two-hundred-mesh sieve. Taking 10g of dried electroplating sludge, adding 50mL of 2mol/L nitric acid, stirring for 2h, and filtering to obtain filtrate, namely electroplating sludge pickle liquor, wherein the pH value is 4.
(2) Adding 100mg of bacterial cellulose (high-fiber coconut, purchased from Hainan Cocos food Co., Ltd.) into the electroplating sludge pickle liquor obtained in the step (1), and stirring for 4 hours;
(3) carrying out suction filtration on the solution to obtain a composite material precursor;
(4) and drying the composite material precursor, calcining at 900 ℃ for 5h (the heating rate is 5 ℃/min) in a nitrogen-argon mixed atmosphere, and cooling to obtain the Sn/Fe @ C composite material.
As can be seen from fig. 9, in the composite material prepared from the bacterial cellulose, the metallic tin simple substance is aggregated into relatively large micron-scale small particles, and as can be seen from fig. 10, compared with the nano-scale composite material prepared from the bacillus subtilis, the electrochemical performance is far different, and the specific capacity is only about 420 mAh/g.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for preparing a lithium ion battery cathode material by using electroplating sludge is characterized by comprising the following preparation steps:
(1) adding inorganic acid into the electroplating sludge, uniformly stirring, and filtering to obtain electroplating sludge pickle liquor containing tin and iron;
(2) inoculating bacillus subtilis into the culture solution, and culturing to obtain a bacillus subtilis solution;
(3) adding the acid leaching solution of the electroplating sludge obtained in the step (1) into the bacillus subtilis liquid obtained in the step (2), and uniformly mixing to obtain a mixed solution;
(4) filtering the mixed solution obtained in the step (3), and drying to obtain a precursor of the bacillus subtilis and tin-iron composite material;
(5) calcining the precursor of the composite material of the bacillus subtilis and the tin iron at high temperature in an inert or reducing atmosphere to obtain the Sn/Fe @ C composite material;
wherein the pH value of the electroplating sludge pickle liquor in the step (1) is 4-8.
2. The method for preparing the lithium ion battery anode material by using the electroplating sludge according to claim 1, wherein the method comprises the following steps:
the concentration of the inorganic acid in the step (1) is 0.1-3 mol/L.
3. The method for preparing the lithium ion battery anode material by using the electroplating sludge according to claim 1, wherein the method comprises the following steps:
the inoculation amount of the bacillus subtilis in the step (2) is 1-10%.
4. The method for preparing the lithium ion battery anode material by using the electroplating sludge according to claim 1, wherein the method comprises the following steps:
mixing in the step (3) by oscillating or stirring; the mixing time is 1-24 h.
5. The method for preparing the lithium ion battery anode material by using the electroplating sludge according to claim 1, wherein the method comprises the following steps:
the ratio of the bacillus subtilis liquid to the electroplating sludge acid leaching liquid in the step (3) by volume is 1: (0.1-5).
6. The method for preparing the lithium ion battery anode material by using the electroplating sludge according to claim 1, wherein the method comprises the following steps:
the high-temperature calcination in the step (5) is carried out by heating to 500-900 ℃ at a heating rate of 1-15 ℃/min for 1-10 h.
7. The method for preparing the lithium ion battery anode material by using the electroplating sludge according to claim 1, wherein the method comprises the following steps:
the inorganic acid in the step (1) is one or at least two of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
the filtration in the step (4) is one or at least two of gravity filtration, centrifugal filtration and vacuum filtration;
the drying in the step (4) is one or at least two of normal pressure drying, vacuum drying and freeze drying;
the inert or reducing atmosphere in the step (5) is one or a mixture of at least two of nitrogen, argon and hydrogen.
8. A lithium ion battery negative electrode material is characterized in that:
the method for preparing the lithium ion battery anode material by using the electroplating sludge as claimed in any one of claims 1 to 7.
9. The method for preparing the lithium ion battery anode material by using electroplating sludge according to any one of claims 1 to 7 or the application of the lithium ion battery anode material according to claim 8 in the field of lithium ion batteries.
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