CN110224115A - A kind of lithium ion battery negative material and the preparation method and application thereof - Google Patents
A kind of lithium ion battery negative material and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110224115A CN110224115A CN201810175305.4A CN201810175305A CN110224115A CN 110224115 A CN110224115 A CN 110224115A CN 201810175305 A CN201810175305 A CN 201810175305A CN 110224115 A CN110224115 A CN 110224115A
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- Prior art keywords
- lithium ion
- ion battery
- electroplating sludge
- battery negative
- negative material
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000010802 sludge Substances 0.000 claims abstract description 60
- 238000009713 electroplating Methods 0.000 claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000021110 pickles Nutrition 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 244000063299 Bacillus subtilis Species 0.000 claims description 31
- 244000025254 Cannabis sativa Species 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 20
- 239000002054 inoculum Substances 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 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
- 239000007789 gas Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 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
- 238000010792 warming Methods 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 19
- 241000894006 Bacteria Species 0.000 abstract description 17
- 239000002243 precursor Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- -1 iron ion Chemical class 0.000 abstract description 2
- 239000011366 tin-based material Substances 0.000 abstract description 2
- 239000011135 tin Substances 0.000 description 31
- 239000001963 growth medium Substances 0.000 description 17
- 229910052718 tin Inorganic materials 0.000 description 13
- 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
- 238000007747 plating Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011780 sodium chloride Substances 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
- 229940041514 candida albicans extract Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000012138 yeast extract Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 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
- 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
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation 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
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 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
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- H01M10/05—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 present invention provides a kind of lithium ion battery negative materials and the preparation method and application thereof.Bacterium is added to absorption tin, iron ion in pickle liquor by the present invention, by stirring, being obtained by filtration composite material precursor, precursor is placed under atmosphere of inert gases again and is calcined, Sn/Fe@C composite cathode material for lithium ion cell is obtained, preparation process is simple, easy to operate, easily controllable；Both the recycling of achievable electroplating sludge, can also solve the expansion issues of tin-based material, to realize the technology path of waste higher value application.Lithium ion battery negative material of the invention can the fine volume change that must alleviate metallic tin in charge and discharge process, avoid the volume expansion of the tin in charge and discharge process, acquired material has superior cyclical stability and higher capacity；When composite material is used for lithium cell negative pole material, good chemical property is shown, the demand of Vehicles Collected from Market is more able to satisfy.
Description
Technical field
The present invention relates to a kind of method that metal is extracted in recycling in electroplating sludge, in particular to a kind of negative electrode of lithium ion battery
Material and the preparation method and application thereof.
Background technique
With the rapid development of electroplating industry, electroplating sludge amount also in rapid growth.Containing a large amount of in electroplating sludge
Metal (tin, iron, copper, chromium, nickel, zinc etc.).If electroplating sludge not dealt carefully with, it will to the health of our mankind
Fatal threat is generated with ecological environment.Therefore harmless treatment electroplating sludge and high-valued recycling heavy metal therein become industry
Interior popular research direction.
Currently, processing electroplating sludge method mainly include the following types:
1, it is directly filled after sludge dewatering.
2, pyrometallurgical smelting is handled.
3, ion exchange membrane.
4, ammonia leaching process.
5, the acid-hatching of young eggs.
6, bioanalysis.
But because containing a large amount of nondegradable heavy metals in electroplating sludge, the above processing method is lacked there are biggish
Point and risk, such as: processing cost height, Yi Fasheng secondary environmental pollution etc..
Contain the metallic elements such as a large amount of tin, iron, copper in electroplating sludge.Wherein tin has high theoretical capacity 994mAh/g,
It is a kind of lithium ion battery negative material with long-range application prospect.It has low deintercalation platform, battery theoretical capacity high
The advantages that.But there is also in charge and discharge process, tin is easy to happen volume expansion, and electrode material powder of detached causes battery to hold
The shortcomings that reduction of amount and cycle performance are deteriorated, so being difficult to realize commercially produce application.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of utilization electroplating sludge preparation
The method of lithium ion battery negative material.The characteristic for absorbing heavy metal is selected to handle in electroplating sludge pickle liquor using bacterium
Heavy metal ion.Bacterium is added to absorption tin, iron ion in pickle liquor, by stirring, being filtered by vacuum before obtaining composite material
Body, then precursor is placed under atmosphere of inert gases and is calcined, obtain Sn/Fe@C composite cathode material for lithium ion cell.It utilizes
Withered grass Bacillussubtilis serves as tin in carrier selective extraction recycling electroplating sludge and prepares high performance lithium ionic cell cathode material.Both
The recycling of achievable electroplating sludge, can also solve the expansion issues of tin-based material, to realize waste higher value application
Technology path.
Another object of the present invention is to provide the lithium ion battery negative materials as made from the method.Described
Metal ion battery cathode composite material avoids the volume expansion of the tin in charge and discharge process, when composite material is negative for lithium electricity
When the material of pole, good chemical property is shown.
A further object of the present invention is to provide the applications of the method or the lithium ion battery negative material.
The purpose of the invention is achieved by the following technical solution:
A method of lithium ion battery negative material, including following preparation step are prepared using electroplating sludge:
(1) inorganic acid is added in electroplating sludge, stirs evenly, stanniferous, iron electroplating sludge pickle liquor is obtained by filtration；
(2) withered grass Bacillussubtilis is inoculated among culture solution, culture obtains withered grass Bacillussubtilis bacterium solution；
(3) by the resulting electroplating sludge pickle liquor of step (1) add to the resulting withered grass Bacillussubtilis bacterium solution of step (2) it
In, it is uniformly mixed, obtains mixed solution；
(4) mixed solution obtained by step (3) is filtered, is dried to obtain the forerunner of withered grass Bacillussubtilis Yu tin iron composite material
Body；
(5) by the presoma of the withered grass Bacillussubtilis and tin iron composite material under inertia or reducing atmosphere high temperature
Calcining, can be obtained Sn/Fe@C composite.
The pH of pickle liquor described in step (1) is preferably 4~8.
Inorganic acid described in step (1) be preferably hydrochloric acid, sulfuric acid, nitric acid, in one in phosphoric acid or at least two.
The concentration of inorganic acid described in step (1) is preferably 0.1~3mol/L.
The time of stirring described in step (1) is preferably 1~3h.
The inoculum concentration of withered grass Bacillussubtilis described in step (2) is preferably 1%~10%.
Culture solution described in step (2) is preferably prepared by the following method and is obtained: 10g tryptone, 5g yeast are mentioned
Object, 5g sodium chloride are taken, 1L deionized water is dissolved in, stirs evenly.
The time of culture described in step (2) is preferably 12~for 24 hours.
Mixing described in step (3) preferably passes through oscillation or stirring is mixed；The mixed time is preferably 1
~for 24 hours.
Withered grass Bacillussubtilis bacterium solution in step (3) and electroplating sludge pickle liquor preferably 1:(0.1~5 by volume) match
Than；Further preferably by 1:(1~3 by volume) proportion.
Filtering described in step (4) is preferably one of gravity filtration, centrifugal filtration and vacuum filter or at least two
Kind.
Drying described in step (4) is preferably one of constant pressure and dry, vacuum drying, freeze-drying or at least two
Kind.
Inertia described in step (5) or reducing atmosphere are preferably one of nitrogen, argon gas, hydrogen or at least two
The gaseous mixture of kind composition.
High-temperature calcination described in step (5) is preferably warming up to 500~900 DEG C with the heating rate of 1~15 DEG C/min
Calcine 1~10h.
The lithium ion battery negative material as made from the method.
The application of the preparation method or the lithium ion battery negative material in field of lithium ion battery.
The present invention has the following advantages and effects with respect to the prior art:
(1) industrial waste electroplating sludge higher value application, processing material used are microorganism by the present invention, and source is wide
It is general, it is low in cost.The purpose of waste higher value application may be implemented, and can solve environmental problem.This research is by electroplating sludge
Higher value application, only harmless treatment electroplating sludge does not provide new thinking, also provides for preparation electrochemical energy storage materials
New approaches.
(2) preparation process of the present invention is simple, easy to operate, easily controllable.
(3) the part graphite alkylene after calcination at high temperature of the bacterium in composite material prepared by the present invention, be conducive to ion and
Electron-transport.
(4) in Sn/Fe@C composite prepared by the present invention, the carrier of metallic tin iron is worked as using bacterium, can be fine
Alleviate volume change of the metallic tin in charge and discharge process, acquired material has superior cyclical stability and higher appearance
Amount is 1A g in current density-1Under specific capacity up to 620.4mAh g-1, and specific capacity conservation rate is big after 1000 circulations
In 95%.With it is other prepare the method for electrode material compared with, such as application No. is CN201310715142.1 and application number
Technical solution documented by the patent document of CN200910193554.7, method of the invention have superior cyclical stability and
High specific capacity is more able to satisfy the demand of Vehicles Collected from Market.
Detailed description of the invention
Fig. 1 is the XRD spectra of Sn-Fe@C composite obtained in embodiment 1.
Fig. 2 is the SEM figure of Sn-Fe@C composite obtained in embodiment 1.
Fig. 3 is to be assembled into button cell in current density using Sn-Fe@C composite obtained in embodiment 2 to be
First charge-discharge curve graph when 0.1A/g.
Fig. 4 is the SEM figure of Sn-Fe@C composite obtained in embodiment 2.
Fig. 5 is that Sn-Fe@C composite obtained is assembled into button cell and follows when current density is 1A/g in embodiment 3
Ring performance map.
Fig. 6 is that Sn-Fe@C composite obtained is assembled into times of the button cell under different current densities in embodiment 3
Rate performance map.
Fig. 7 is the XRD diagram of Sn-Fe@C composite obtained in embodiment 4.
Fig. 8 is the SEM figure of Sn-Fe@C composite obtained in embodiment 4.
Fig. 9 is that composite material SEM figure is made in comparative example 2.
Figure 10 is to prepare composite material in comparative example 2 to dress up button cell cycle performance figure when current density is 1A/g.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) it configures culture medium: weighing 10g tryptone, 5g yeast extract, 5g sodium chloride, be dissolved in 1L deionized water, stir
It mixes uniformly, forms stable clear solution.
(2) electroplating sludge pickle liquor: electroplating sludge is placed in baking oven, 90 DEG C, 12 hours dry, and grinding crosses 200
Mesh sieve.Electroplating sludge after taking 10g dry, is added 50mL 1mol/L hydrochloric acid, stirs 2h, and filtering gained filtrate is that plating is dirty
Mud acid immersion liquid, pH 5.4.
(3) inoculated bacteria: with 1% inoculum concentration by withered grass Bacillussubtilis strain (Bacillus subtilis ATCC-
6633) it is inoculated on culture medium prepared by step (1), is placed in constant temperature oscillation shaking table and activates 12h；
(4) expand culture: the withered grass Bacillussubtilis after step (3) activation is inoculated in by step (1) institute with 1% inoculum concentration
It on the culture medium of preparation, is placed in constant temperature oscillation shaking table and cultivates 12h, obtain withered grass Bacillussubtilis bacterium solution；
(5) electroplating sludge pickle liquor obtained by step (2) is added in the bacteria culture media after step (4) expand culture, acid
The volume ratio of immersion liquid and culture medium is 1:1, and stirs 6h；
(6) above-mentioned solution is filtered, obtains composite material precursor；
(7) composite material precursor is dried, under an argon atmosphere 600 DEG C of calcining 2h (heating rate is 10 DEG C/min),
It is cooling to obtain Sn/Fe C composite.
The physical and chemical performance characterization of Sn/ bacterium composite material obtained is shown in Fig. 1 and Fig. 2, and Fig. 1 is the Sn/Fe@C for preparing compound
The XRD spectrum of material, Fig. 2 are the SEM figures of the Sn/Fe@C composite prepared in embodiment 1.
XRD shows in Sn/Fe@C composite manufactured in the present embodiment that there are simple substance tin and ferro-tin alloy, SEM shows multiple
The pattern of condensation material is good, and tin and ferro-tin alloy are evenly distributed in bacterium surface.
Products therefrom is assembled into button cell and tests its discharge capacity, and charge and discharge are carried out within the scope of 0.01~2.5V.Such as
Fig. 3 show first charge-discharge curve when current density is 0.1A/g.Meanwhile the capacity of composite material reaches 898.2mAh/
g。
Embodiment 2
(1) it configures culture medium: weighing 10g tryptone, 5g yeast extract, 5g sodium chloride, be dissolved in 1L deionized water, stir
It mixes uniformly, forms stable clear solution.
(2) electroplating sludge pickle liquor: electroplating sludge is placed in baking oven, 90 DEG C, 12 hours dry, and grinding crosses 200
Mesh sieve.Electroplating sludge after taking 10g dry, is added 50mL 0.1mol/L nitric acid, stirs 3h, filtering gained filtrate is plating
Sludge pickle liquor, pH 6.8.
(3) inoculated bacteria: with 1% inoculum concentration by withered grass Bacillussubtilis (Bacillus subtilis ATCC-6633)
It is inoculated on culture medium prepared by step (1), is placed in constant temperature oscillation shaking table and activates 12h；
(4) expand culture: microbionation training prepared by step (1) after step (3) being activated with 5% inoculum concentration
It supports on base, is placed in constant temperature oscillation shaking table and cultivates for 24 hours, obtain withered grass Bacillussubtilis bacterium solution；
(5) electroplating sludge pickle liquor obtained by step (2) is added to step (4) and is obtained in withered grass Bacillussubtilis bacterium solution, acid
The volume ratio of immersion liquid and culture medium is 2:1, and stirs 12h；
(6) above-mentioned solution is filtered, obtains composite material precursor；
(7) composite material precursor is dry, 700 DEG C of calcining 2h (heating rate is 7 DEG C/min), cold in a nitrogen atmosphere
But Sn/Fe C composite is obtained.
The physical and chemical performance characterization of Sn/Fe@C composite obtained is shown in that Fig. 4, Fig. 5, Fig. 4 are the Sn/Fe@C composite woods prepared
The SEM of material schemes, and Fig. 4 shows that tin is evenly distributed with tin ferroalloy in bacterium surface.Gained Sn/Fe@C composite is assembled into button
Formula battery, Fig. 5 are cycle performance figure at current density 1A/g, and specific capacity reaches 620.4mAh/g for the first time under the multiplying power,
Specific capacity conservation rate is 95% or more after 1000 circulations.
Embodiment 3
1) it configures culture medium: weighing 10g tryptone, 5g yeast extract, 5g sodium chloride, be dissolved in 1L deionized water, stir
It mixes uniformly, forms stable clear solution.
(2) electroplating sludge pickle liquor: electroplating sludge is placed in baking oven, 90 DEG C, 12 hours dry, and grinding crosses 200
Mesh sieve.Electroplating sludge after taking 10g dry, is added 50mL 2mol/L hydrochloric acid, stirs 2h, and filtering gained filtrate is that plating is dirty
Mud acid immersion liquid, pH 8.0.
(3) inoculated bacteria: with 1% inoculum concentration by withered grass Bacillussubtilis (Bacillus subtilis ATCC-6633)
It is inoculated on culture medium prepared by step (1), is placed in constant temperature oscillation shaking table and activates 12h；
(4) expand culture: with 10% inoculum concentration by the microbionation after step (3) activation prepared by step (1)
On culture medium, it is placed in constant temperature oscillation shaking table and cultivates for 24 hours；
(5) electroplating sludge pickle liquor obtained by step (2) is added in the bacteria culture media after step (4) expand culture, electricity
The volume ratio for plating sludge pickle liquor and culture medium is 3:1, and is stirred for 24 hours；
(6) above-mentioned solution is filtered, obtains composite material precursor；
(7) composite material precursor is dry, it is forged for lower 500 DEG C in nitrogen hydrogen mixed gas atmosphere (95% nitrogen, 5% hydrogen)
It burns 2h (heating rate is 5 DEG C/min), it is cooling to obtain Sn/Fe C composite.
Gained Sn/Fe@C composite is assembled into button cell and tests its charge/discharge capacity, in 0.01~2.5V range
Interior progress cycle life test.It is illustrated in figure 6 obtained high rate performance of the button cell under different current densities, Cong Tuzhong
It can be seen that this Sn/Fe@C composite has superior high rate performance.
Comparative example 1
(1) it configures culture medium: weighing 10g tryptone, 5g yeast extract, 5g sodium chloride, be dissolved in 1L deionized water, stir
It mixes uniformly, forms stable clear solution.
(2) electroplating sludge pickle liquor: electroplating sludge is placed in baking oven, 90 DEG C, 12 hours dry, and grinding crosses 200
Mesh sieve.Electroplating sludge after taking 10g dry, is added 50mL 2mol/L nitric acid, stirs 2h, and filtering gained filtrate is that plating is dirty
Mud acid immersion liquid, pH 5.4.
(3) inoculated bacteria: with 5% inoculum concentration by withered grass Bacillussubtilis (Bacillus subtilis ATCC-6633)
It is inoculated on culture medium prepared by step (1), is placed in constant temperature oscillation shaking table and activates 12h；
(4) expand culture: the bacillus subtilis after step (3) activation is inoculated in by step (1) with 10% inoculum concentration
It on prepared culture medium, is placed in constant temperature oscillation shaking table and cultivates for 24 hours, obtain withered grass Bacillussubtilis bacterium solution；
(5) electroplating sludge pickle liquor obtained by step (2) is added in the withered grass Bacillussubtilis bacterium solution that step (4) obtain, electricity
The volume ratio for plating sludge pickle liquor and culture medium is 3:1, and stirs 12h；
(6) above-mentioned solution is filtered, obtains composite material precursor；
(7) composite material precursor is dry, 900 DEG C of calcining 5h (heating rates 1 under nitrogen argon gas mixed atmosphere
DEG C/min), it is cooling to obtain Sn/Fe C composite.
The XRD spectrum of obtained Sn/Fe@C composite is as shown in fig. 7, prove composite material by the retrieval of PDF card
The existence form of middle tin is metal simple-substance tin.But by the SEM result of Fig. 8 it will be seen that composite material is not protected
Original pattern of bacterium is held, bacillus pattern is destroyed, very big to composite material Electrochemical Performances.
Comparative example 2
(1) electroplating sludge pickle liquor: electroplating sludge is placed in baking oven, 90 DEG C, 12 hours dry, and grinding crosses 200
Mesh sieve.Electroplating sludge after taking 10g dry, is added 50mL 2mol/L nitric acid, stirs 2h, and filtering gained filtrate is that plating is dirty
Mud acid immersion liquid, pH 4.
(2) step (1) is added in 100mg bacteria cellulose (high microsteping coconut is purchased from Hainan Yeguo Food Co., Ltd)
Obtained in electroplating sludge pickle liquor, and stir 4h；
(3) above-mentioned solution is filtered, obtains composite material precursor；
(4) composite material precursor is dry, 900 DEG C of calcining 5h (heating rates 5 under nitrogen argon gas mixed atmosphere
DEG C/min), it is cooling to obtain Sn/Fe C composite.
From fig. 9, it can be seen that using bacteria cellulose preparation composite material in, metallic tin simple substance, which has been gathered into, to be compared
The little particle of big micron level, from fig. 10 it can be seen that answering compared to the Nano grade prepared using bacillus subtilis
Condensation material, chemical property differ farther out, and specific capacity only has 420mAh/g or so.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method for preparing lithium ion battery negative material using electroplating sludge, which is characterized in that including preparing step as follows
It is rapid:
(1) inorganic acid is added in electroplating sludge, stirs evenly, stanniferous, iron electroplating sludge pickle liquor is obtained by filtration；
(2) withered grass Bacillussubtilis is inoculated among culture solution, culture obtains withered grass Bacillussubtilis bacterium solution；
(3) the resulting electroplating sludge pickle liquor of step (1) is added among the resulting withered grass Bacillussubtilis bacterium solution of step (2), is mixed
It closes uniformly, obtains mixed solution；
(4) mixed solution obtained by step (3) is filtered, is dried to obtain the presoma of withered grass Bacillussubtilis Yu tin iron composite material；
(5) by the presoma of the withered grass Bacillussubtilis and tin iron composite material, high temperature is forged under inertia or reducing atmosphere
It burns, Sn/Fe@C composite can be obtained.
2. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
The pH of electroplating sludge pickle liquor described in step (1) is 4~8.
3. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
The concentration of inorganic acid described in step (1) is 0.1~3mol/L.
4. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
The inoculum concentration of withered grass Bacillussubtilis described in step (2) is 1%~10%.
5. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
Mixing described in step (3) is mixed by oscillation or stirring；The mixed time be 1~for 24 hours.
6. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
Withered grass Bacillussubtilis bacterium solution in step (3) and electroplating sludge pickle liquor 1:(0.1~5 by volume) proportion.
7. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
High-temperature calcination described in step (5) be with the heating rate of 1~15 DEG C/min be warming up to 500~900 DEG C calcining 1~
10h。
8. the method according to claim 1 for preparing lithium ion battery negative material using electroplating sludge, it is characterised in that:
Inorganic acid described in step (1) be hydrochloric acid, sulfuric acid, nitric acid, in one in phosphoric acid or at least two；
Step is filtered into one of gravity filtration, centrifugal filtration and vacuum filter or at least two described in (4)；
Drying described in step (4) is one of constant pressure and dry, vacuum drying, freeze-drying or at least two；
Inertia described in step (5) or reducing atmosphere are one of nitrogen, argon gas, hydrogen or at least two compositions
Gaseous mixture.
9. a kind of lithium ion battery negative material, it is characterised in that:
It is prepared by the method according to any one of claims 1 to 8 for preparing lithium ion battery negative material using electroplating sludge
It obtains.
10. the method or right according to any one of claims 1 to 8 for preparing lithium ion battery negative material using electroplating sludge
It is required that application of the lithium ion battery negative material described in 9 in field of lithium ion battery.
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