CN103035897A - Tin-based composite spherical hard charcoal microsphere negative electrode material of lithium battery, and preparation method for negative electrode material - Google Patents
Tin-based composite spherical hard charcoal microsphere negative electrode material of lithium battery, and preparation method for negative electrode material Download PDFInfo
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- CN103035897A CN103035897A CN2012105578165A CN201210557816A CN103035897A CN 103035897 A CN103035897 A CN 103035897A CN 2012105578165 A CN2012105578165 A CN 2012105578165A CN 201210557816 A CN201210557816 A CN 201210557816A CN 103035897 A CN103035897 A CN 103035897A
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- lithium battery
- tinbase
- cathode material
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- 239000004005 microsphere Substances 0.000 title claims abstract description 92
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000003610 charcoal Substances 0.000 title abstract description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000007773 negative electrode material Substances 0.000 title abstract 7
- 239000000463 material Substances 0.000 claims abstract description 33
- 229920002472 Starch Polymers 0.000 claims abstract description 27
- 239000008107 starch Substances 0.000 claims abstract description 27
- 235000019698 starch Nutrition 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 229910021385 hard carbon Inorganic materials 0.000 claims description 100
- 239000010406 cathode material Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004575 stone Substances 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 6
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910006404 SnO 2 Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000005087 graphitization Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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 relates to a tin-based composite spherical hard charcoal microsphere negative electrode material of a lithium battery, and a preparation method for the negative electrode material, and belongs to the technical field of negative electrode materials of lithium batteries. The tin-based composite spherical hard charcoal microsphere negative electrode material of the lithium battery is prepared from tin-containing precursors and spherical hard charcoal spheres according the mass ratio of 1:2 to 1:50, wherein the spherical hard charcoal spheres are prepared from starch-based hard charcoal. SnO2 is filled into holes in the spherical hard charcoal microsphere negative electrode material, so that on one hand, stress generated by SnO2 deformation can be absorbed by the charcoal layers at the periphery of the holes and the circulating stability of the SnO2 is guaranteed, and on the other hand, the gap in the spherical hard charcoal can be utilized, the space utilization rate and the volume energy density of the material are increased and the effect of killing two birds with one stone is achieved.
Description
Technical field
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, more particularly, the present invention relates to hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical and preparation method thereof, belong to the lithium ion battery negative material technical field.
Background technology
Day by day universal along with Portable digital product, and the rise of electric motor car, extensive energy-storage system, lithium rechargeable battery is large with its energy density, operating voltage is high, have extended cycle life, pollution-free, the advantage such as security performance is good, represent widely application prospect, more and more be subject to the attention of researcher and enterprise.
The research of lithium cell cathode material is one of key technology of lithium ion battery always.In general, lithium cell cathode material is divided into charcoal negative pole and non-charcoal negative pole two large classes.Wherein, carbon cathode material especially graphite carbon negative material causes worldwide broad research and exploitation with its structural stability and good cycle performance highly, becomes the lithium ion battery negative material that occupies at present mainstream market.But the capacity of its 372mAh/g is excessively low, more and more can not satisfying the market the requirement of development.And because graphite has layer structure, therefore when lithium ion enter layer with layer the gap in, will make graphite volumetric expansion about 10%.If charge rate is too fast, effect is too violent, will cause peeling off of graphite, even the short circuit blast.Why charge rate is slow for general commercially available battery, is exactly for fear of this danger mainly.Therefore, people's diversion to other material, such as soft charcoal, hard charcoal, charcoal/silicon composite, metal oxide etc.
SnO
2A kind of N-shaped semi-conducting material of broadband, as lithium ion battery negative material, SnO
2Having high 781mAh/g theoretical capacity, is that the twice of conventional graphite negative pole is many.But SnO
2Change in volume is very large in charge and discharge process, and this can cause electrode structural deterioration in cyclic process, the capacity sharp-decay, and this has limited the Commercialization application of this material undoubtedly.The methods such as in order to overcome this defective of tin base cathode, the researcher has carried out a large amount of work, and employing nanometer and other materials are compound make great progress.
Patent 201010132581.6 has prepared SnO
2Then composite material with phenolic resins further obtains SnO by heat treatment
2With the composite material of phenolic resins pyrolysis carbon, this material has good cyclicity and specific capacity.But phenolic resins pyrolysis carbon itself is a kind of hard carbon material, and degree of graphitization is low, poorly conductive.And the technology path of this patent has determined that the composite material heat treatment temperature is not higher than 630 ℃, and the RESEARCH OF PYROCARBON defective that forms under such temperature is many, poorly conductive, and this can improve the irreversible capacity of negative material undoubtedly, reduces the high rate performance of negative material.
Patent 201210094245 uses plasma apparatus to prepare the nanometer tin particle, uses carbonaceous gas as carbon source again, uses the vapor phase deposition legal system for tin/carbon composite.Its first reversible specific capacity reach 620mAh/g.This material is as lithium ion battery negative material, has higher embedding/take off lithium capacity density and cyclical stability.But because this process using is plasma method and vapour deposition process, so equipment and technology is comparatively complicated, realizes relatively difficulty of volume production, and cost also is difficult to control.
Reported a kind of spherical hard carbon cathode material with nucleocapsid structure in the patent 201110360282.2, this negative material is made by the graphitization layer on the hard charcoal of starch base and surface, this material surface passes through the catalyzed graphitization processing that is lower than 1500 ℃ and has formed very thin graphitization layer, and inside has kept hard carbon structure; As lithium cell cathode material, have the specific capacity height, have extended cycle life the advantages such as good rate capability.Because this material is by starch material system, and the grain structure that has kept well starch, therefore starch granules interior molecules relatively more loose " acromphalus " position of arranging will form hole in carbonization process, and the spherical firmly carbon cathode material inside that finally obtains has certain hollow structure.Hollow space is not contributed capacity, but has occupied volume, is disadvantageous to the raising of battery volume energy density therefore.
Summary of the invention
It is very large that the present invention is intended to solve in the prior art in the tin ash negative material charge and discharge process change in volume, cause electrode structural deterioration in cyclic process, hole in capacity sharp-decay and the spherical hard carbon microsphere cathode material, reduced the problem of battery volume energy density, provide a kind of lithium battery tinbase complex spherical hard carbon cathode material, can fill up the hole in the spherical hard carbon microspheres, improve the problem of battery volume energy density, avoid simultaneously in the tin ash negative material charge and discharge process change in volume very large, cause electrode structural deterioration in cyclic process, the problem of capacity sharp-decay.
Another object of the present invention provides the preferred preparation method of the hard carbon cathode material of a kind of above-mentioned lithium battery tinbase complex spherical.
In order to realize the foregoing invention purpose, its concrete technical scheme is as follows:
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the hard carbon microsphere cathode material of described lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, and adopting stanniferous presoma and spherical hard carbon microspheres is that 1:2-1:50 makes according to mass ratio again.
Preferably, the hard carbon microspheres of sphere of the present invention is that the hard charcoal of starch base is nuclear, and graphite is the nucleocapsid structure of shell.
Preferably, sn-containing compound of the present invention is SnCl
45H
2O, SnCl
23H
2O or Na
2SnO
33H
2O.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical adopts first the hard charcoal of starch base to make spherical hard carbon microspheres, it is characterized in that: the hard carbon microspheres of described sphere is comprised the processing of following processing step:
A, stanniferous precursor is dissolved in the solvent, the solution of preparation mass concentration 1-10% obtains stanniferous precursor solution;
B, be that 1:2-1:50 takes by weighing spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in the stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor that obtains to step B are regulated pH to 8-10, and stirring reaction, obtain reactant liquor;
D, the reactant liquor that uses the method treatment step C of centrifugal, filtration or suction filtration to obtain with solvent wash 3-5 time, obtain solids of sedimentation with the precipitation that obtains;
E, by solids of sedimentation: the PTFE mass ratio is that 1:0.15-1:0.05 takes by weighing the PTFE emulsion, by solids of sedimentation: the deionized water quality is than taking by weighing deionized water for 1:0.8-1:2, precipitated solid, PTFE emulsion, deionized water are mixed, stir, obtain mixed slurry;
F, the mixed slurry striking liquid film that uses blade applicator that step e is obtained, then oven dry obtains film;
G, film that step F is obtained obtain SnO at 180-250 ℃ of heat treatment 1-5h
2/ spherical hard carbon microspheres composite negative pole material is the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
Preferably, the present invention is in steps A and step D, and described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
Preferably, the present invention is in step C, and described stirring refers to stir with rotating speed 100-1500r/min under 0-80 ℃ of temperature.
Preferably, the present invention is in step C, and the time of described stirring reaction is 1-5h.
Preferably, the present invention is in step F, and described is to carry out striking at glass plate at glass plate use blade applicator with the mixed slurry striking liquid film that step e obtains.
Preferably, the present invention is in step F, and described thickness of liquid film is 100-200 μ m.
The present invention is in step G, and tube furnace, box type furnace or rotary furnace are used in described heat treatment.
A kind of lithium battery that adopts the hard carbon microsphere cathode material of above-mentioned lithium battery tinbase complex spherical to make.
The above-mentioned method for preparing lithium battery is this area common process.
The useful technique effect that the present invention brings:
1, the present invention uses SnO
2The hole of the hard carbon microsphere cathode material of sphere inside is filled, can utilize on the one hand hole charcoal layer on every side to absorb SnO
2The stress that deformation produces guarantees SnO
2Cyclical stability; The space of the hard charcoal of sphere inside can be used on the other hand, improve space availability ratio and the volume energy density of material, reach the effect of killing two birds with one stone;
2, the moulding process of the present invention's use is prepared a kind of SnO
2/ spherical hard carbon microspheres composite negative pole material, this material has had both SnO
2Height ratio capacity, and excellent cycle performance, high rate performance, the cryogenic property of hard carbon material, therefore, it is large that this composite negative pole material has specific capacity, and efficient is high first, and high rate performance is good, the advantage that fail safe and cycle life are good has been agreed with the right demand of new type lithium ion battery;
3, the cost of material used of the inventive method is cheap, and the source is abundant, is easy to realize large-scale industrial production; After tested, the SnO of the present invention's preparation
2/ spherical hard carbon microspheres composite negative pole material film thickness is 20-120 μ m.This composite material first capacity reaches 630mAh/g, and through 100 circulation volume conservation rates more than 80%, and capacity still is not less than 500mAh/g in the large multiplying power discharging situation of 10C, has shown good high rate performance.
Embodiment
Embodiment 1
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the hard carbon microsphere cathode material of described lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, and adopting stanniferous presoma and spherical hard carbon microspheres is that 1:2 makes according to mass ratio again.
Embodiment 2
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the hard carbon microsphere cathode material of described lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, and adopting stanniferous presoma and spherical hard carbon microspheres is that 1:50 makes according to mass ratio again.
Embodiment 3
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the hard carbon microsphere cathode material of described lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, and adopting stanniferous presoma and spherical hard carbon microspheres is that 1:26 makes according to mass ratio again.
Embodiment 4
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the hard carbon microsphere cathode material of described lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, and adopting stanniferous presoma and spherical hard carbon microspheres is that 1:37 makes according to mass ratio again.
Embodiment 5
On the basis of embodiment 1-4, preferred:
The hard carbon microspheres of described sphere is that the hard charcoal of starch base is nuclear, and graphite is the nucleocapsid structure of shell.
Described sn-containing compound is SnCl
45H
2O, SnCl
23H
2O or Na
2SnO
33H
2O.
Embodiment 6
The preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical adopts first the hard charcoal of starch base to make spherical hard carbon microspheres, the hard carbon microspheres of described sphere is comprised the processing of following processing step:
A, stanniferous precursor is dissolved in the solvent, the solution of preparation mass concentration 1% obtains stanniferous precursor solution;
B, be that 1:2 takes by weighing spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in the stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor that obtains to step B are regulated pH to 8, and stirring reaction, obtain reactant liquor;
D, the reactant liquor that uses the method treatment step C of centrifugal, filtration or suction filtration to obtain with solvent wash 3 times, obtain solids of sedimentation with the precipitation that obtains;
E, by solids of sedimentation: the PTFE mass ratio is that 1:0.05 takes by weighing the PTFE emulsion, and by solids of sedimentation: the deionized water quality, stirs precipitated solid, PTFE emulsion, deionized water mixing than taking by weighing deionized water for 1:0.8, obtains mixed slurry;
F, the mixed slurry striking liquid film that uses blade applicator that step e is obtained, then oven dry obtains film;
G, film that step F is obtained obtain SnO at 180 ℃ of heat treatment 1h
2/ spherical hard carbon microspheres composite negative pole material is the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
Embodiment 7
The preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical adopts first the hard charcoal of starch base to make spherical hard carbon microspheres, the hard carbon microspheres of described sphere is comprised the processing of following processing step:
A, stanniferous precursor is dissolved in the solvent, the solution of preparation mass concentration 10% obtains stanniferous precursor solution;
B, be that 1:50 takes by weighing spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in the stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor that obtains to step B are regulated pH to 10, and stirring reaction, obtain reactant liquor;
D, the reactant liquor that uses the method treatment step C of centrifugal, filtration or suction filtration to obtain with solvent wash 5 times, obtain solids of sedimentation with the precipitation that obtains;
E, by solids of sedimentation: the PTFE mass ratio is that 1:0.15 takes by weighing the PTFE emulsion, and by solids of sedimentation: the deionized water quality, stirs precipitated solid, PTFE emulsion, deionized water mixing than taking by weighing deionized water for 1:2, obtains mixed slurry;
F, the mixed slurry striking liquid film that uses blade applicator that step e is obtained, then oven dry obtains film;
G, film that step F is obtained obtain SnO at 250 ℃ of heat treatment 5h
2/ spherical hard carbon microspheres composite negative pole material is the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
Embodiment 8
The preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical adopts first the hard charcoal of starch base to make spherical hard carbon microspheres, the hard carbon microspheres of described sphere is comprised the processing of following processing step:
A, stanniferous precursor is dissolved in the solvent, the solution of preparation mass concentration 5.5% obtains stanniferous precursor solution;
B, be that 1:26 takes by weighing spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in the stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor that obtains to step B are regulated pH to 9, and stirring reaction, obtain reactant liquor;
D, the reactant liquor that uses the method treatment step C of centrifugal, filtration or suction filtration to obtain with solvent wash 4 times, obtain solids of sedimentation with the precipitation that obtains;
E, by solids of sedimentation: the PTFE mass ratio is that 1:0.1 takes by weighing the PTFE emulsion, and by solids of sedimentation: the deionized water quality, stirs precipitated solid, PTFE emulsion, deionized water mixing than taking by weighing deionized water for 1:1.4, obtains mixed slurry;
F, the mixed slurry striking liquid film that uses blade applicator that step e is obtained, then oven dry obtains film;
G, film that step F is obtained obtain SnO at 215 ℃ of heat treatment 3h
2/ spherical hard carbon microspheres composite negative pole material is the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
Embodiment 9
The preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical adopts first the hard charcoal of starch base to make spherical hard carbon microspheres, the hard carbon microspheres of described sphere is comprised the processing of following processing step:
A, stanniferous precursor is dissolved in the solvent, the solution of preparation mass concentration 8.5% obtains stanniferous precursor solution;
B, be that 1:37 takes by weighing spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in the stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor that obtains to step B are regulated pH to 8.5, and stirring reaction, obtain reactant liquor;
D, the reactant liquor that uses the method treatment step C of centrifugal, filtration or suction filtration to obtain with solvent wash 4 times, obtain solids of sedimentation with the precipitation that obtains;
E, by solids of sedimentation: the PTFE mass ratio is that 1:0.08 takes by weighing the PTFE emulsion, and by solids of sedimentation: the deionized water quality, stirs precipitated solid, PTFE emulsion, deionized water mixing than taking by weighing deionized water for 1:0.9, obtains mixed slurry;
F, the mixed slurry striking liquid film that uses blade applicator that step e is obtained, then oven dry obtains film;
G, film that step F is obtained obtain SnO at 200 ℃ of heat treatment 2.5h
2/ spherical hard carbon microspheres composite negative pole material is the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
Embodiment 10
On the basis of embodiment 6-9:
Preferably, in steps A and step D, described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
Preferably, in step C, described stirring refers to stir with rotating speed 100r/min under 0 ℃ of temperature.
Preferably or further, in step C, the time of described stirring reaction is 1h.
Preferably, in step F, described is to carry out striking at glass plate at glass plate use blade applicator with the mixed slurry striking liquid film that step e obtains.
Preferably or further, in step F, described thickness of liquid film is 100 μ m.
Embodiment 11
On the basis of embodiment 6-9:
Preferably, in steps A and step D, described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
Preferably, in step C, described stirring refers to stir with rotating speed 1500r/min under 80 ℃ of temperature.
Preferably or further, in step C, the time of described stirring reaction is 5h.
Preferably, in step F, described is to carry out striking at glass plate at glass plate use blade applicator with the mixed slurry striking liquid film that step e obtains.
Preferably or further, in step F, described thickness of liquid film is 200 μ m.
Embodiment 12
On the basis of embodiment 6-9:
Preferably, in steps A and step D, described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
Preferably, in step C, described stirring refers to stir with rotating speed 800r/min under 40 ℃ of temperature.
Preferably or further, in step C, the time of described stirring reaction is 3h.
Preferably, in step F, described is to carry out striking at glass plate at glass plate use blade applicator with the mixed slurry striking liquid film that step e obtains.
Preferably or further, in step F, described thickness of liquid film is 150 μ m.
Embodiment 13
On the basis of embodiment 6-9:
Preferably, in steps A and step D, described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
Preferably, in step C, described stirring refers to stir with rotating speed 1000r/min under 75 ℃ of temperature.
Preferably or further, in step C, the time of described stirring reaction is 2.5h.
Preferably, in step F, described is to carry out striking at glass plate at glass plate use blade applicator with the mixed slurry striking liquid film that step e obtains.
Preferably or further, in step F, described thickness of liquid film is 120 μ m.
Embodiment 14
The preparation method of spherical hard carbon microspheres is this area common process, now is exemplified below:
Starch is joined in the heating furnace, under inert atmosphere, rise to 100-300 ℃ with the heating rate of 0.1-10 ℃/min and heat-treat 1-72h, then rising to 700-1500 ℃ with the heating rate of 0.5-30 ℃/min carries out charing to material and processes 0.2-5h, and under inert atmosphere, be cooled to room temperature, obtain the spherical hard carbon microspheres of starch base.
Preparation method with spherical hard carbon microspheres of nucleocapsid structure is this area common process, now is exemplified below:
A, the hard carbon microspheres of preparation starch base;
B, take the soluble-salt of transition metal as catalyst, water or absolute ethyl alcohol are that solvent preparation mass concentration is 0.5～30% catalyst solution;
C, the starch-based carbon microsphere that steps A is obtained join in the catalyst solution of step B preparation of 10～20 times of volumes, stir dipping 0.2～24h;
D, adopt the mode of centrifugal, filtration or suction filtration that starch-based carbon microsphere is separated with catalyst solution, starch-based carbon microsphere is dried in drying box;
E, the starch-based carbon microsphere of impregnated catalyst and oven dry is risen to 1000～1500 ℃ with the heating rate of 0.5～10 ℃/min carry out catalyzed graphitization and process 1～24h under inert atmosphere, and under inert atmosphere, be cooled to room temperature;
F, materials'use acid elution that step e is obtained 3～8 times then use deionized water washing 3～5 times, and oven dry obtains namely that the surface has the graphitization layer and innerly is the hard carbon microsphere cathode material of lithium battery nucleocapsid structure of hard carbon structure.
Claims (10)
1. hard carbon microsphere cathode material of lithium battery tinbase complex spherical, it is characterized in that: the hard carbon microsphere cathode material of described lithium battery tinbase complex spherical adopts the starch base hard carbon to make spherical hard carbon microballoon, and adopting stanniferous presoma and spherical hard carbon microballoon is that 1:2-1:50 makes according to mass ratio again.
2. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1 is characterized in that: described spherical hard carbon microballoon is that the starch base hard carbon is nuclear, and graphite is the nucleocapsid structure of shell.
3. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1, it is characterized in that: described sn-containing compound is SnCl
45H
2O, SnCl
23H
2O or Na
2SnO
33H
2O.
4. the preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1, adopt first the starch base hard carbon to make spherical hard carbon microballoon, it is characterized in that: described spherical hard carbon microballoon is comprised the processing of following processing step:
A, stanniferous precursor is dissolved in the solvent, the solution of preparation mass concentration 1-10% obtains stanniferous precursor solution;
B, by stanniferous precursor and spherical hard carbon microspheres quality than taking by weighing spherical hard carbon microballoon for 1:2-1:50, join in the stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor that obtains to step B are regulated pH to 8-10, and stirring reaction, obtain reactant liquor;
D, the reactant liquor that uses the method treatment step C of centrifugal, filtration or suction filtration to obtain with solvent wash 3-5 time, obtain solids of sedimentation with the precipitation that obtains;
E, by solids of sedimentation: the PTFE mass ratio is that 1:0.15-1:0.05 takes by weighing the PTFE emulsion, by solids of sedimentation: the deionized water quality is than taking by weighing deionized water for 1:0.8-1:2, precipitated solid, PTFE emulsion, deionized water are mixed, stir, obtain mixed slurry;
F, the mixed slurry striking liquid film that uses blade applicator that step e is obtained, then oven dry obtains film;
G, film that step F is obtained obtain SnO at 180-250 ℃ of heat treatment 1-5h
2/ spherical hard carbon microspheres composite negative pole material is the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
5. the preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 4, it is characterized in that: in steps A and step D, described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
6. the preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 4, it is characterized in that: in step C, described stirring refers to stir with rotating speed 100-1500r/min under 0-80 ℃ of temperature.
7. according to claim 4 or the preparation method of the hard carbon microsphere cathode material of 6 described a kind of lithium battery tinbase complex sphericals, it is characterized in that: in step C, the time of described stirring reaction is 1-5h.
8. the preparation method of the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 4, it is characterized in that: in step F, described is to carry out striking at glass plate at glass plate use blade applicator with the mixed slurry striking liquid film that step e obtains.
9. according to claim 4 or the preparation method of the hard carbon microsphere cathode material of 8 described a kind of lithium battery tinbase complex sphericals, it is characterized in that: in step F, described thickness of liquid film is 100-200 μ m.
10. lithium battery that adopts the hard carbon microsphere cathode material of lithium battery tinbase complex spherical claimed in claim 1 to make.
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| CN112331836A (en) * | 2020-11-23 | 2021-02-05 | 华中科技大学 | Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof |
| CN114927648A (en) * | 2022-05-06 | 2022-08-19 | 广东凯金新能源科技股份有限公司 | SnO (stannic oxide) -based 2 Artificial electrolyte interface film modified hard carbon negative electrode and preparation method thereof |
| CN114927648B (en) * | 2022-05-06 | 2023-06-09 | 广东凯金新能源科技股份有限公司 | SnO-based 2 Artificial electrolyte interface film modified hard carbon negative electrode and preparation method thereof |
| CN116799219A (en) * | 2023-08-25 | 2023-09-22 | 浙江华宇钠电新能源科技有限公司 | Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle |
| CN116799219B (en) * | 2023-08-25 | 2023-12-15 | 浙江华宇钠电新能源科技有限公司 | Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle |
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