CN103035897B - 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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- CN103035897B CN103035897B CN201210557816.5A CN201210557816A CN103035897B CN 103035897 B CN103035897 B CN 103035897B CN 201210557816 A CN201210557816 A CN 201210557816A CN 103035897 B CN103035897 B CN 103035897B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 96
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003610 charcoal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 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 31
- 229920002472 Starch Polymers 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 235000019698 starch Nutrition 0.000 claims abstract description 27
- 239000008107 starch Substances 0.000 claims abstract description 27
- 229910021385 hard carbon Inorganic materials 0.000 claims description 96
- 239000010406 cathode material Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 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 19
- 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
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 14
- 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
- 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
- 239000011521 glass Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 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
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 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 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
- 239000003054 catalyst Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005087 graphitization Methods 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
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research 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
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011796 hollow space material Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible 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
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
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- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
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 technical field of lithium ion battery negative.
Background technology
Day by day universal along with Portable digital product, and electric motor car, large-scale energy storage system rise, the advantages such as lithium rechargeable battery is large with its energy density, operating voltage is high, have extended cycle life, pollution-free, security performance is good, present application prospect widely, be more and more 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 the large class of non-charcoal negative pole two.Wherein, carbon cathode material especially graphite carbon negative material causes worldwide extensive research and development with the structural stability of its height and good cycle performance, becomes the lithium ion battery negative material occupying mainstream market at present.But the capacity of its 372mAh/g is too low, the requirement of market development more and more can not be met.And there is layer structure due to graphite, therefore when in the gap that lithium ion enters layer and layer, graphite volumetric expansion about 10% will be made.If charge rate is too fast, effect is too violent, will cause peeling off of graphite, even short circuit blast.Why charge rate is slow for general commercial battery, is exactly mainly in order to avoid this danger.Therefore, people's diversion on other material, such as soft charcoal, hard charcoal, charcoal/silicon composite, metal oxide etc.
SnO
2a kind of n-type semiconductor 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
2in charge and discharge process, change in volume is very large, and this can cause electrode structural deterioration in cyclic process, capacity sharp-decay, and this limits the Commercialization application of this material undoubtedly.In order to overcome this defect of tin base cathode, researcher has carried out a large amount of work, adopts the method such as nanometer and other materials compound, makes great progress.
Patent 201010132581.6 has prepared SnO
2composite material with phenolic resins, then obtains SnO further 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 determines composite material heat treatment temperature not higher than 630 DEG C, the RESEARCH OF PYROCARBON defect formed at such temperatures is many, poorly conductive, and this can improve the irreversible capacity of negative material undoubtedly, reduces the high rate performance of negative material.
The patent 201210094245 nanometer tin particle that used plasma apparatus to prepare, then use carbonaceous gas as carbon source, with the standby tin/carbon composite of vapor phase deposition legal system.Its first reversible specific capacity reach 620mAh/g.This material, as lithium ion battery negative material, has higher embedding/de-lithium capacity density and cyclical stability.But what adopt due to this technique is plasma method and vapour deposition process, and therefore equipment and technology is comparatively complicated, realizes volume production more difficult, cost is also difficult to control.
A kind of spherical hard carbon cathode material with nucleocapsid structure is reported in patent 201110360282.2, this negative material is made up of the graphitic layers on the hard charcoal of starch base and surface, this material surface defines very thin graphitic layers through the catalyzed graphitization process lower than 1500 DEG C, and inside maintains hard carbon structure; As lithium cell cathode material, there is specific capacity high, have extended cycle life, the advantages such as good rate capability.Because this material is by starch material, and maintain the grain structure of starch well, therefore " acromphalus " position that the arrangement of starch granules interior molecules is relatively more loose in carbonization process will form hole, and the spherical hard carbon cathode material inside finally obtained has certain hollow structure.Hollow space does not contribute capacity, but occupies volume, is therefore disadvantageous to the raising of battery volume energy density.
Summary of the invention
It is very large that the present invention to be intended to solve in prior art change in volume in tin ash negative material charge and discharge process, cause electrode structural deterioration in cyclic process, hole in capacity sharp-decay and spherical hard carbon microsphere cathode material, reduce the problem of battery volume energy density, there is provided a kind of lithium battery tinbase complex spherical hard carbon cathode material, the hole in spherical hard carbon microspheres can be filled up, improve the problem of battery volume energy density, avoid change in volume in tin ash negative material charge and discharge process very large simultaneously, cause electrode structural deterioration in cyclic process, the problem of capacity sharp-decay.
Another object of the present invention is to provide 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 foregoing invention object, 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 described hard carbon microsphere cathode material of lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, then adopts stanniferous presoma and spherical hard carbon microspheres to be that 1:2-1:50 makes according to mass ratio.
Preferably, spherical hard carbon microspheres of the present invention is the hard charcoal of starch base is core, 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.
A preparation method for the hard carbon microsphere cathode material of lithium battery tinbase complex spherical, first adopts the hard charcoal of starch base to make spherical hard carbon microspheres, it is characterized in that: the process described spherical hard carbon microspheres being carried out comprising following processing step:
A, be dissolved in solvent by stanniferous precursor, the solution of preparation mass concentration 1-10%, obtains stanniferous precursor solution;
B, be that 1:2-1:50 takes spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor obtained to step B, regulate pH to 8-10, and stirring reaction, obtain reactant liquor;
D, use centrifugal, filter or reactant liquor that the method treatment step C of suction filtration obtains, by the precipitating solvent washing 3-5 time obtained, obtain solids of sedimentation;
E, by solids of sedimentation: PTFE mass ratio is that 1:0.15-1:0.05 takes PTFE emulsion, by solids of sedimentation: deionized water quality takes deionized water than for 1:0.8-1:2, by precipitated solid, PTFE emulsion, deionized water mixing, stir, obtain mixed slurry;
F, the mixed slurry striking liquid film using blade applicator step e to be obtained, then dry, obtain film;
G, the film that step F obtained, at 180-250 DEG C of heat treatment 1-5h, obtain SnO
2/ spherical hard carbon microspheres composite negative pole material and 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 stirs with rotating speed 100-1500r/min at 0-80 DEG C 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 the described mixed slurry striking liquid film using blade applicator step e to be obtained on a glass carries out striking on a glass.
Preferably, the present invention is in step F, and described thickness of liquid film is 100-200 μm.
The present invention is in step G, and described heat treatment uses tube furnace, box type furnace or rotary furnace.
A kind of lithium battery adopting the hard carbon microsphere cathode material of above-mentioned lithium battery tinbase complex spherical to make.
The above-mentioned method preparing lithium battery is this area common process.
The Advantageous Effects that the present invention brings:
1, the present invention uses SnO
2by the holes filling of spherical hard carbon microsphere cathode material inside, the layer of charcoal around hole can be utilized to absorb SnO on the one hand
2the stress that deformation produces, ensures SnO
2cyclical stability; The space of spherical hard charcoal 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 that the present invention uses prepares a kind of SnO
2/ spherical hard carbon microspheres composite negative pole material, this materials combine 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 efficiency is high first, and high rate performance is excellent, fail safe and the good advantage of cycle life, agreed with the demand that new type lithium ion battery is right;
3, the low in raw material price used of the inventive method, abundance, is easy to realize large-scale industrial and produces; After tested, the SnO for preparing of the present invention
2/ spherical hard carbon microspheres composite negative pole material film thickness is 20-120 μm.This composite material first capacity reaches 630mAh/g, and through 100 circulation volume conservation rates more than 80%, and in the large multiplying power discharging situation of 10C, capacity is still not less than 500mAh/g, shows excellent 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 described hard carbon microsphere cathode material of lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, then adopts stanniferous presoma and spherical hard carbon microspheres to be that 1:2 makes according to mass ratio.
embodiment 2
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the described hard carbon microsphere cathode material of lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, then adopts stanniferous presoma and spherical hard carbon microspheres to be that 1:50 makes according to mass ratio.
embodiment 3
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the described hard carbon microsphere cathode material of lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, then adopts stanniferous presoma and spherical hard carbon microspheres to be that 1:26 makes according to mass ratio.
embodiment 4
The hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical, it is characterized in that: the described hard carbon microsphere cathode material of lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, then adopts stanniferous presoma and spherical hard carbon microspheres to be that 1:37 makes according to mass ratio.
embodiment 5
On the basis of embodiment 1-4, preferred:
Described spherical hard carbon microspheres is the hard charcoal of starch base is core, 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
A preparation method for the hard carbon microsphere cathode material of lithium battery tinbase complex spherical, first adopts the hard charcoal of starch base to make spherical hard carbon microspheres, described spherical hard carbon microspheres is carried out the process comprising following processing step:
A, be dissolved in solvent by stanniferous precursor, the solution of preparation mass concentration 1%, obtains stanniferous precursor solution;
B, be that 1:2 takes spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor obtained to step B, regulate pH to 8, and stirring reaction, obtain reactant liquor;
D, use centrifugal, filter or reactant liquor that the method treatment step C of suction filtration obtains, the precipitating solvent obtained is washed 3 times, obtains solids of sedimentation;
E, by solids of sedimentation: PTFE mass ratio is that 1:0.05 takes PTFE emulsion, by solids of sedimentation: precipitated solid, PTFE emulsion, deionized water, than taking deionized water for 1:0.8, mix, stir, obtain mixed slurry by deionized water quality;
F, the mixed slurry striking liquid film using blade applicator step e to be obtained, then dry, obtain film;
G, the film that step F obtained, at 180 DEG C of heat treatment 1h, obtain SnO
2/ spherical hard carbon microspheres composite negative pole material and the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
embodiment 7
A preparation method for the hard carbon microsphere cathode material of lithium battery tinbase complex spherical, first adopts the hard charcoal of starch base to make spherical hard carbon microspheres, described spherical hard carbon microspheres is carried out the process comprising following processing step:
A, be dissolved in solvent by stanniferous precursor, the solution of preparation mass concentration 10%, obtains stanniferous precursor solution;
B, be that 1:50 takes spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor obtained to step B, regulate pH to 10, and stirring reaction, obtain reactant liquor;
D, use centrifugal, filter or reactant liquor that the method treatment step C of suction filtration obtains, the precipitating solvent obtained is washed 5 times, obtains solids of sedimentation;
E, by solids of sedimentation: PTFE mass ratio is that 1:0.15 takes PTFE emulsion, by solids of sedimentation: precipitated solid, PTFE emulsion, deionized water, than taking deionized water for 1:2, mix, stir, obtain mixed slurry by deionized water quality;
F, the mixed slurry striking liquid film using blade applicator step e to be obtained, then dry, obtain film;
G, the film that step F obtained, at 250 DEG C of heat treatment 5h, obtain SnO
2/ spherical hard carbon microspheres composite negative pole material and the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
embodiment 8
A preparation method for the hard carbon microsphere cathode material of lithium battery tinbase complex spherical, first adopts the hard charcoal of starch base to make spherical hard carbon microspheres, described spherical hard carbon microspheres is carried out the process comprising following processing step:
A, be dissolved in solvent by stanniferous precursor, the solution of preparation mass concentration 5.5%, obtains stanniferous precursor solution;
B, be that 1:26 takes spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor obtained to step B, regulate pH to 9, and stirring reaction, obtain reactant liquor;
D, use centrifugal, filter or reactant liquor that the method treatment step C of suction filtration obtains, the precipitating solvent obtained is washed 4 times, obtains solids of sedimentation;
E, by solids of sedimentation: PTFE mass ratio is that 1:0.1 takes PTFE emulsion, by solids of sedimentation: precipitated solid, PTFE emulsion, deionized water, than taking deionized water for 1:1.4, mix, stir, obtain mixed slurry by deionized water quality;
F, the mixed slurry striking liquid film using blade applicator step e to be obtained, then dry, obtain film;
G, the film that step F obtained, at 215 DEG C of heat treatment 3h, obtain SnO
2/ spherical hard carbon microspheres composite negative pole material and the hard carbon microsphere cathode material of lithium battery tinbase complex spherical of the present invention.
embodiment 9
A preparation method for the hard carbon microsphere cathode material of lithium battery tinbase complex spherical, first adopts the hard charcoal of starch base to make spherical hard carbon microspheres, described spherical hard carbon microspheres is carried out the process comprising following processing step:
A, be dissolved in solvent by stanniferous precursor, the solution of preparation mass concentration 8.5%, obtains stanniferous precursor solution;
B, be that 1:37 takes spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor obtained to step B, regulate pH to 8.5, and stirring reaction, obtain reactant liquor;
D, use centrifugal, filter or reactant liquor that the method treatment step C of suction filtration obtains, the precipitating solvent obtained is washed 4 times, obtains solids of sedimentation;
E, by solids of sedimentation: PTFE mass ratio is that 1:0.08 takes PTFE emulsion, by solids of sedimentation: precipitated solid, PTFE emulsion, deionized water, than taking deionized water for 1:0.9, mix, stir, obtain mixed slurry by deionized water quality;
F, the mixed slurry striking liquid film using blade applicator step e to be obtained, then dry, obtain film;
G, the film that step F obtained, at 200 DEG C of heat treatment 2.5h, obtain SnO
2/ spherical hard carbon microspheres composite negative pole material and 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 stirs with rotating speed 100r/min at 0 DEG C of temperature.
Preferably or further, in step C, the time of described stirring reaction is 1h.
Preferably, in step F, the described mixed slurry striking liquid film using blade applicator step e to be obtained on a glass carries out striking on a glass.
Preferably or further, in step F, described thickness of liquid film is 100 μm.
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 stirs with rotating speed 1500r/min at 80 DEG C of temperature.
Preferably or further, in step C, the time of described stirring reaction is 5h.
Preferably, in step F, the described mixed slurry striking liquid film using blade applicator step e to be obtained on a glass carries out striking on a glass.
Preferably or further, in step F, described thickness of liquid film is 200 μm.
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 stirs with rotating speed 800r/min at 40 DEG C of temperature.
Preferably or further, in step C, the time of described stirring reaction is 3h.
Preferably, in step F, the described mixed slurry striking liquid film using blade applicator step e to be obtained on a glass carries out striking on a glass.
Preferably or further, in step F, described thickness of liquid film is 150 μm.
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 stirs with rotating speed 1000r/min at 75 DEG C of temperature.
Preferably or further, in step C, the time of described stirring reaction is 2.5h.
Preferably, in step F, the described mixed slurry striking liquid film using blade applicator step e to be obtained on a glass carries out striking on a glass.
Preferably or further, in step F, described thickness of liquid film is 120 μm.
embodiment 14
The preparation method of spherical hard carbon microspheres is this area common process, is now exemplified below:
Starch is joined in heating furnace, rise to 100-300 DEG C with the heating rate of 0.1-10 DEG C/min under an inert atmosphere and heat-treat 1-72h, then rise to 700-1500 DEG C with the heating rate of 0.5-30 DEG C/min and charing process 0.2-5h is carried out to material, and be cooled to room temperature under an inert atmosphere, obtain the spherical hard carbon microspheres of starch base.
The preparation method with the spherical hard carbon microspheres of nucleocapsid structure is this area common process, is now exemplified below:
A, the hard carbon microspheres of preparation starch base;
B, with the soluble-salt of transition metal for catalyst, water or absolute ethyl alcohol be solvent preparation mass concentration be the catalyst solution of 0.5 ~ 30%;
C, starch-based carbon microsphere steps A obtained join in the catalyst solution of step B preparation of 10 ~ 20 times of volumes, stir, dipping 0.2 ~ 24h;
D, adopt centrifugal, to filter or starch-based carbon microsphere is separated with catalyst solution by the mode of suction filtration, starch-based carbon microsphere is dried in drying box;
E, by impregnated catalyst and the starch-based carbon microsphere of drying rise to 1000 ~ 1500 DEG C with the heating rate of 0.5 ~ 10 DEG C/min under an inert atmosphere and carry out catalyzed graphitization process 1 ~ 24h, and be cooled to room temperature under an inert atmosphere;
F, the materials'use acid elution that step e obtained 3 ~ 8 times, then use deionized water washing 3 ~ 5 times, dry, and namely obtains surface and have graphitic layers and the inner hard carbon microsphere cathode material of lithium battery nucleocapsid structure for hard carbon structure.
Claims (7)
1. the hard carbon microsphere cathode material of lithium battery tinbase complex spherical, it is characterized in that: the described hard carbon microsphere cathode material of lithium battery tinbase complex spherical adopts the hard charcoal of starch base to make spherical hard carbon microspheres, then adopts stanniferous precursor and spherical hard carbon microspheres to be that 1:2-1:50 makes according to mass ratio; Described spherical hard carbon microspheres is the hard charcoal of starch base is core, and graphite is the nucleocapsid structure of shell; Described stanniferous precursor is SnCl
45H
2o, SnCl
23H
2o or Na
2snO
33H
2o;
The described hard carbon microsphere cathode material of lithium battery tinbase complex spherical is obtained by following methods:
First adopt the hard charcoal of starch base to make spherical hard carbon microspheres, then described spherical hard carbon microspheres carried out the process comprising following processing step:
A, be dissolved in solvent by stanniferous precursor, the solution of preparation mass concentration 1-10%, obtains stanniferous precursor solution;
B, be that 1:2-1:50 takes spherical hard carbon microspheres by stanniferous precursor and spherical hard carbon microspheres mass ratio, join in stanniferous precursor solution, obtain mixed solution;
C, the mixed solution and dripping ammoniacal liquor obtained to step B, regulate pH to 8-10, and stirring reaction, obtain reactant liquor;
D, use centrifugal, filter or reactant liquor that the method treatment step C of suction filtration obtains, by the precipitating solvent washing 3-5 time obtained, obtain solids of sedimentation;
E, by solids of sedimentation: PTFE mass ratio is that 1:0.15-1:0.05 takes PTFE emulsion, by solids of sedimentation: deionized water quality takes deionized water than for 1:0.8-1:2, by precipitated solid, PTFE emulsion, deionized water mixing, stir, obtain mixed slurry;
F, the mixed slurry striking liquid film using blade applicator step e to be obtained, then dry, obtain film;
G, the film that step F obtained, at 180-250 DEG C of heat treatment 1-5h, obtain SnO
2/ spherical hard carbon microspheres composite negative pole material, the i.e. hard carbon microsphere cathode material of lithium battery tinbase complex spherical.
2. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1, is characterized in that: in steps A and step D, and described solvent is water, ethanol, acetone, formic acid, n-hexane or toluene.
3. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1, is characterized in that: in step C, and described stirring refers to stirs with rotating speed 100-1500r/min at 0-80 DEG C of temperature.
4. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1 or 3, is characterized in that: in step C, the time of described stirring reaction is 1-5h.
5. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1, is characterized in that: in step F, and mixed slurry striking liquid film step e obtained carries out striking on a glass.
6. the hard carbon microsphere cathode material of a kind of lithium battery tinbase complex spherical according to claim 1 or 5, it is characterized in that: in step F, described thickness of liquid film is 100-200 μm.
7. the lithium battery adopting the hard carbon microsphere cathode material of lithium battery tinbase complex spherical according to claim 1 to make.
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| CN108365207B (en) * | 2018-03-27 | 2021-01-19 | 北京化工大学 | Lithium ion battery cathode stannous oxide/carbon composite material and synthesis method thereof |
| CN110707290B (en) * | 2019-10-18 | 2022-08-05 | 河南电池研究院有限公司 | Preparation method of flexible lithium ion battery negative electrode with sandwich-like structure |
| 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 |
| 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 |
| 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 |
| CN118538913B (en) * | 2024-07-25 | 2024-10-18 | 国科炭美新材料(湖州)有限公司 | Hard carbon microsphere negative electrode material and preparation method and application thereof |
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| CN102386382A (en) * | 2011-11-03 | 2012-03-21 | 大连理工大学 | CMK-5 type mesoporous carbon-nano inorganic substance composite material, preparation method and application thereof |
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| FR2939786B1 (en) * | 2008-12-11 | 2011-03-25 | Arkema France | PROCESS FOR MANUFACTURING COMPOSITE SNO2 MATERIAL AND CARBON NANOTUBES AND / OR CARBON NANOFIBERS, MATERIAL OBTAINED BY THE PROCESS, ELECTRODE FOR LITHIUM BATTERY COMPRISING SAID MATERIAL. |
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| CN102386383A (en) * | 2011-11-15 | 2012-03-21 | 中国东方电气集团有限公司 | Lithium battery hard carbon microsphere cathode material with core-shell structure and preparation method thereof |
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