CN102208617A - Method for preparing cathode active substance of lithium ion secondary cells - Google Patents
Method for preparing cathode active substance of lithium ion secondary cells Download PDFInfo
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- CN102208617A CN102208617A CN2010101410147A CN201010141014A CN102208617A CN 102208617 A CN102208617 A CN 102208617A CN 2010101410147 A CN2010101410147 A CN 2010101410147A CN 201010141014 A CN201010141014 A CN 201010141014A CN 102208617 A CN102208617 A CN 102208617A
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 17
- 239000013543 active substance Substances 0.000 title abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000006479 redox reaction Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 67
- 229910052710 silicon Inorganic materials 0.000 claims description 40
- 239000010703 silicon Substances 0.000 claims description 40
- 239000007773 negative electrode material Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 24
- 150000004696 coordination complex Chemical class 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 235000013312 flour Nutrition 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000013467 fragmentation Methods 0.000 claims description 4
- 238000006062 fragmentation reaction Methods 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000002210 silicon-based material Substances 0.000 abstract description 22
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000002905 metal composite material Substances 0.000 abstract 2
- 238000002386 leaching Methods 0.000 abstract 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 38
- 229910052802 copper Inorganic materials 0.000 description 34
- 239000010949 copper Substances 0.000 description 34
- 239000010408 film Substances 0.000 description 22
- 229910052744 lithium Inorganic materials 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 230000008569 process Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 8
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- 239000010410 layer Substances 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002409 silicon-based active material Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
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- 150000003376 silicon Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Abstract
The invention provides a method for preparing a cathode active substance of lithium ion cells, comprising the following concrete steps of: 1) mixing a silicon powder and an active metal powder, sintering under protective gas to melt the active metal powder and letting the melted active metal powder coat on the surface of the silicon material so as to obtain a silicon-active metal composite; 2) crushing the silicon-active metal composite prepared from Step 1, sieving, followed by addition of a copper salt solution, performing an oxidation reduction reaction to obtain a turbid solution; 3) adding acetic acid or hydrochloric acid into the turbid solution from the Step 2, adjusting the pH value within the pH range of 4-6, leaching and drying to obtain the cathode active substance for secondary cells. The active metal is zinc or aluminum. The method provided by the invention has advantages of simple technology and less discharge of waste materials; and the cathode active substance prepared by the method has advantages of high conductivity, stable structure, high specific capacity and good cycle performance.
Description
Technical field
The invention belongs to field of batteries, relate in particular to the preparation method who the present invention relates to a kind of active material for negative pole of Li-ion secondary battery.
Background technology
Along with the fast development of portable electronic equipment, very urgent for the demand of the good lithium ion battery of specific energy height, cycle performance.Negative material is mainly based on graphite in the business-like at present lithium ion battery.Yet, although graphite can show good performance as lithium ion battery negative material, because the restriction (372 MAH/gram) of its theoretical specific capacity has limited the further raising of lithium ion battery specific energy.And silicon receives much attention because of it has high theoretical lithium storage content (reaching 4000 MAH/grams).
Yet, though silicon materials have high specific capacity, but because it can produce huge change in volume in the doff lithium process, it is bulk effect, thereby itself and conductive materials are on every side lost to electrically contact, thereby it is electroactive to make material lose, and then produce a large amount of irreversible capacities, cause reduce the useful life of silicium cathode, simultaneously, because silicon materials repeatedly change in volume in the doff lithium process makes that the SEI film of negative terminal surface is destroyed repeatedly and forms, from having quickened the decay of battery capacity.
At present, the method for improving the silicon materials cycle performance has a lot, such as adopting nano-silicon as negative electrode active material.Nano-silicon can show better electrochemical performance as active material in initial circulation several times, but carrying out along with circulation, agglomeration can take place in nano-silicon, thereby capacity attenuation is very fast in follow-up cyclic process, and adopt nano-silicon to cost an arm and a leg as negative material, even if the cycle performance in the time of improving it as negative pole, the possibility of large-scale commercial applicationsization is also little.
Amorphous silicon can show good cyclical stability and very high reversible specific capacity (reach 1000 MAHs/more than the gram), but its preparation method difficulty.Mainly be to deposit the unbodied silicon thin film of one deck at collection liquid surface at present by the method that adopts physical chemistry vapour deposition (PVD) or chemical vapor deposition (CVD).Because the silica-base material of this method preparation can show excellent electrochemical properties really, so become the focus of present research, but in fact, although amorphous silicon film can show high reversible specific capacity and good cycle performance, but silicon fiml can not deposit too thick, because silicon materials are very crisp, the blocked up meeting of rete causes the silicon materials on the pole piece to fall material, also be that silicon materials come off from collector, thereby can only adopt thin thickness to carry out correlative study (general single face thickness is difficult to above 7 microns).If but silicon fiml is too thin, then because very few dressing amount, the reversible capacity that makes collector on the unit are to provide is still very little, can't be applied to reality at all.
There is the people active metal and silicon is compound in the prior art by ball grinding method, preparation lithium ion battery negative electrode active material, a kind of negative material is disclosed among concrete preparation method such as the CN101409345A, this negative active core-shell material contains material with carbon element and silicon based composite material, it is characterized in that, described silicon based composite material contains component A and B component, and described component A is an elemental silicon; Described B component is two or more the metal in copper, titanium, aluminium, iron, zinc and the cobalt, the preparation method of this silicon based composite material mixes component A and B component for comprising, obtain silicon based composite material, described component A is an elemental silicon, and described B component is two or more the metal in copper, titanium, aluminium, iron, zinc and the cobalt; Then described silicon based composite material and material with carbon element are mixed, obtain negative active core-shell material, the method that wherein said component A and B component mix is that ball milling mixes.This method adopts simple chemical combination method to be prepared from, in the metal of employing as aluminium etc., in negative pole embedding lithium process can and electrolyte generation negative reaction, can reduce the cycle performance of material to a certain extent.
Summary of the invention
The present invention is for solving cathode material preparation method complexity in the prior art, and the technical problem that the negative material cyclical stability is low, irreversible capacity is big of preparation provides a kind of preparation method of lithium ion battery negative material, and this method comprises:
1) silica flour is mixed with the active metal powder, under inert atmosphere conditions, heats, make the fusing of active metal powder, and be coated on the silicon materials surface, obtain silicon the active metal complex;
2) with prepared silicon in the step 1 active metal complex fragmentation, after sieving, add in the aqueous solution of mantoquita, redox reaction takes place, obtain turbid liquid;
3) add acetic acid or hydrochloric acid in the turbid liquid in step 2, pH is adjusted to 4-6, after suction filtration and the oven dry, obtain the secondary battery cathode material then; Described active metal is zinc or aluminium.
The negative electrode active material of method preparation provided by the present invention prepares the conductivity height, Stability Analysis of Structures, and the specific capacity height, good cycle, and negative electrode active material preparation method provided by the present invention also have advantage of simple technology.
Embodiment
A kind of lithium ion battery silicium cathode preparation methods is provided among the present invention
This method specifically comprises:
1) with silica flour and active metal powder, and under the protective gas condition sintering, make the fusing of active metal powder, and be coated on the silicon materials surface, obtain silicon the active metal complex;
2) with prepared silicon in the step 1 active metal complex fragmentation, after sieving, add the aqueous solution of mantoquita, redox reaction takes place, obtain turbid liquid;
3) add acetic acid or hydrochloric acid in the turbid liquid in step 2, pH is adjusted to 4-6, after suction filtration and the oven dry, obtain negative-electrode active material for secondary battery then;
Described active metal is zinc or aluminium.
The weight ratio of silica flour and active metal powder is 1～9: 1 in the above-mentioned steps 1, is 2～5: 1 under the preferable case.
The present inventor finds by a large amount of experiments, compared with prior art, the preparation method of negative electrode active material provided by the invention, reduced negative electrode active material irreversible capacity, improve its cyclical stability.The silicium cathode material exists irreversible capacity big as lithium ion battery negative material in the prior art, the defective of cycle performance difference, mainly be because, the huge change in volume in doff lithium process first of disclosed negative electrode active material in the prior art, make that the electric guiding systems in the pole piece is destroyed, thereby part silicon is lost activity, cause the most of capacity of battery to discharge, promptly produced a large amount of irreversible capacities first; Simultaneously, because silicon volume in follow-up doff lithium cyclic process expands and contraction makes that pole piece top layer SEI film is destroyed repeatedly, thereby electrolyte can be penetrated into active material inside, and various side reactions constantly take place, and makes the non-constant of cycle performance of silicon materials.Improve the performance of silicon materials, on the one hand must set up a stable conductive network, can bear the expansion repeatedly of silicon and be not destroyed, will set up a stable SEI film system on the other hand, the various side reactions that the infiltration of prevention electrolyte causes, the cycle performance of raising pole piece.By adopting metallic copper to coat Si powder to the lithium inertia, can improve conductivity of electrolyte materials, stop the negative reaction of silicon and electrolyte, simultaneously because metallic copper has good ductility, make silicon in the doff lithium process repeatedly in the expansion process, copper still can be coated on silicon powder surface well, makes electric guiding systems still can play consistently its effect, it is electroactive to be unlikely to make the activated silica material to lose, thereby greatly reduces the irreversible capacity first of material.The present invention just is being based on the preparation method of the lithium ion battery negative pole active materials of this thinking design, compared with prior art, the present invention is by regeneration one deck copper film on silica flour, this layer copper film be the energy stable existence in silicon materials doff lithium process, and can play the effect that replaces the SEI film, in traditional graphite cathode system, naturally the SEI film that forms in the initial charge process can stably exist in circulation subsequently always, and this is because what change in volume graphite does not have substantially in the doff lithium process; But when changing the silicium cathode material into, owing to its change in volume huge in the doff lithium process produces very big stress, the effect that the SEI film that the surface forms can't meet with stresses and destroyed tearing, thereby cause electrolyte to infiltrate pole piece inside, the product that side reaction forms similar SEI film further takes place, this layer product is earlier destroyed in circulation subsequently, forms again then again, and this vicious circle repeatedly must make the non-constant of cycle performance of silicium cathode pole piece.Yet,, can ideally solve the problem of silicium cathode pole piece cycle performance difference by plate the copper film of layer of even extension function admirable on silicium cathode pole piece surface.At first, copper film is inertia to electrolyte and lithium, other side reaction can not take place, and can stably exist always; Secondly, its good extension performance can be born the expansion repeatedly of inner silicon materials, can be not destroyed, and ideally with inner active material and electrolyte separately, play a good protection, thereby greatly improved the cyclical stability of pole piece; Once more, this of silicon powder surface layer copper film can also play the effect of collector, improves the conductivity of pole piece, reduces the internal resistance of battery, increases the heavy-current discharge performance of battery.
In the step 1 with the active metal powder with after silica flour mixes, mixture is heated to 20 degree more than the fusing point of active metal, obtain silicon the active metal complex, because the fusing point of silicon is 1410 ℃, and the fusing point of employed active metal is 419.7-660 ℃ among the present invention, more than temperature is heated to the fusing point of active metal of the present invention 20 degrees centigrade the time, melt the active metal, and silica flour does not also arrive fusing point, therefore, the liquation of active metal can form the active metal layer at silicon powder surface under gravity condition, in step 3 with in the step 2 preparation silicon the active metal complex put into copper salt solution, be in the saturated copper salt solution under the preferable case, because the stronger metal of activity can displace the more weak metal simple-substance of this lively type from the salting liquid of the more weak metal of activity, metal activity sequence list is K Ca Na Mg Al Zn Fe Sn Pb H CuHg Ag Pt Au, for the present invention, the position can displace metallic copper at the metal of H front from the salting liquid of the copper of H back, its principle mainly is that the active metal in the salting liquid of copper displacement reaction has taken place, the final result of displacement is to adhere to layer of metal copper at silicon powder surface, and the effect in activated centre has been played in the active metal in this process, but the metal of not every position before H is suitable for the present invention, through a large amount of experiments, the inventor finds that zinc and aluminium are comparatively suitable.
In the step 2 will with in the step 1 preparation silicon active metal complex fragmentation, and sieve, the purpose of sieving be for obtain the less silicon of particle diameter the active metal complex, and the less silicon of particle diameter the active metal complex can in step 3, fully contact with copper salt solution, thereby make more complete that displacement reaction carries out.Among the preparation method of the negative electrode active material that is provided among the present invention, the sieve mesh of sieving of step 2 is preferably 200 orders.
Among the preparation method of copper clad silicon materials of the present invention, the average grain diameter of Si powder and metal dust is 0.01 micron-10 microns, preferred 0.5 micron-3 microns.Because excessive size particles expands repeatedly in the doff lithium cyclic process and shrinks and causes particle cracked easily, and too small particle diameter particle becomes than this height, therefore, select suitable particle diameter.
Among the preparation method of copper clad silicon materials of the present invention, the weight ratio of silicon and active metal is 1～9: 1, and the weight ratio of silicon and active metal is 2～5: 1 under the preferable case.
Among the preparation method of copper clad silicon materials of the present invention, silicon is known stirring of industry or ball milling with the method for mixing of active metal, preferred ball grinding method among the present invention, wherein, the time of ball milling is 1～72h, rotating speed is 100～1000 rev/mins, and can add adequate amount of ethanol, and the weight ratio of ethanol that adds in the mechanical milling process and silicon active metal is 1～2: 1.In mechanical milling process, add ethanol and can improve the dispersiveness of active metal in silica flour.
Among the preparation method of copper clad silicon materials of the present invention, the temperature control active metal fusing point of high-temperature heat treatment silicon active metal mixture is to being higher than 20 ℃ of active metal fusing points, when the active metal was zinc, the temperature of heating was 450-490 ℃, and the time of heating is 0.5 hour-10 hours; When the active metal was Al, the temperature of heating was 650-690 ℃, and the time of heating is 0.5 hour-10 hours, and too high temperature causes active metal high temperature to be evaporated easily, and low excessively temperature is unfavorable for that it evenly is coated to the Si powder surface.Heat treatment time was controlled in 0.1～10 hour, preferably was controlled in 0.5～2 hour.
Among the preparation method of copper clad silicon materials of the present invention, the copper salt solution of selecting for use is compound nantokites soluble in water such as copper sulphate, copper chloride, the concentration of the copper salt solution of preparation is not limit, but preferred its saturated solution, the copper ion solution of high concentration helps it and is reduced, when the aqueous solution of mantoquita is the mantoquita saturated aqueous solution, silicon the weight ratio of active metal complex and mantoquita be 1.1-1.7: 1.
Among the preparation method of copper clad silicon materials of the present invention, also in the process of native copper, temperature is controlled at 20～80 ℃, is 40～60 ℃ under the preferable case in the active metal.
Among the preparation method of copper clad silicon materials of the present invention, treat that copper salt solution all adds the back that finishes and continues to stir 1 hour, make active metal in the turbid liquid, need to add acetic acid or hydrochloric acid the pH value of turbid liquid is controlled at 4-6 by after the abundant reduction.The acetic acid of preferred 0.1 mol or hydrochloric acid, to dissolve the oxidized metallic copper of unreacted active metal and part, when the pH value of turbid liquid is controlled at 4-6, turbid liquid is also dried by suction filtration, finally obtain the lithium ion secondary battery cathode active material, and suction filtration wherein or oven dry are not repeat them here technology known in those skilled in the art.
Among the preparation method of copper clad silicon materials of the present invention; behind the one-tenth copper clad silicon materials to be prepared, better with performance after 900～1300 ℃ of high-temperature process under protective gas, preferred 1000～1200 ℃; heat treatment time is 1～10 hour, and protective gas can be gases such as argon gas or hydrogen.
The present invention also provides a kind of lithium ion secondary battery cathode sheet, and this negative plate comprises conducting base and is positioned at the negative electrode active material layer on conducting base surface, contains the active material by method preparation provided by the invention in negative electrode active material layer.When preparation this kind negative plate, adopt known film-making of oar technology slurry and the compressing tablet of drawing in the industry; The pole piece for preparing needs further copper plating film to handle, and the coating process that is adopted can adopt known plating of industry or PVD technology, and preferred PVD technology because the concrete manufacture craft of above-mentioned negative plate is technology well known in the art, just repeats no more at this.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1
(1) preparation of negative electrode active material
70 gram silica flours (average diameter is 3 microns) are mixed with 10 gram zinc powders (average diameter is 2 microns), pour 200 ml ethanols into, with 250 rev/mins rotating speeds ball milling 24 hours in ball mill (Zhengzhou City prosperous extra large machine-building Co., Ltd), take out oven dry, then, with the material after the oven dry under argon shield, 430 ℃ of heat treatment 1 hour, take out with stove cooling back and to grind, cross 200 mesh sieves, make silicon the active metal complex;
Take by weighing 80 gram cupric sulfate pentahydrate solids, be mixed with saturated solution, then with its with silicon the active metal complex mix, and stirred 1 hour, obtain turbid liquid;
The dilute hydrochloric acid solution that in above-mentioned solution, slowly adds 100 milliliter of 0.1 mol then, turbid liquid pH value is controlled at 5, and suction filtration then is after washed with de-ionized water 3～5 times, take out oven dry, obtain negative-electrode active material for secondary battery A1 by method preparation provided by the present invention.
The preparation of cathode pole piece
With the negative electrode active material A1 of preparation, 85 grams, carbon black 5 gram, carboxymethyl cellulose (CMC) 12 grams join in 900 milliliters of the deionized waters, stir in de-airing mixer then and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, 100 ℃ of following oven dry, roll-ins then, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated the copper film of about 300 nanometers respectively on its two sides by the PVD method, plated the two sides, back and become bronzing, the actual two sides of silicon active material all is wrapped in by copper film in the pole piece of preparation.
The preparation of anode pole piece
100 gram lithium cobalt oxygen, 3 gram binding agent Kynoar and 2 gram conductive agent acetylene blacks are joined in the 50 gram N-methyl pyrrolidones, and de-airing mixer stirs and forms uniform anode sizing agent then.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, 150 ℃ of oven dry, roll-ins then, is sliced into 480 * 44 millimeters positive pole, wherein contain the lithium cobalt oxygen active substances of 8 grams of having an appointment.
The battery equipment
Respectively with the electric core of positive pole, negative pole and a square lithium ion battery of membrane coil coiled of above-mentioned battery, subsequently lithium hexafluoro phosphate is dissolved in by the concentration of 1 mol in the mixed solvent of ethylene carbonate (EC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)=1: 1: 1 and forms nonaqueous electrolytic solution, about 3.5 grams of reservoir quantity in each battery, lithium rechargeable battery E1 is made in sealing.
Embodiment 2
(1) preparation of negative electrode active material
90 gram silica flours are mixed with 10 gram aluminium powders, add 200 ml ethanols simultaneously, with 250 rev/mins rotating speed ball millings 24 hours, take out oven dry then, under argon shield, 670 ℃ of heating 1 hour grind with stove cooling back taking-up with the material after the oven dry, 200 mesh sieves;
Take by weighing 100 gram cupric sulfate pentahydrate solids, be mixed with saturated solution, the material after just sieving then joins in the copper sulphate saturated solution, treats that all adding the back stirred 1 hour, makes sufficient reacting carry out, and obtains turbid liquid;
The dilute acetic acid solution that in above-mentioned turbid liquid, slowly adds 100 milliliter of 0.1 mol; turbid liquid pH is adjusted to 6; stop to stir after continuing to stir half an hour, suction filtration, and with after the washed with de-ionized water 3～5 times; take out oven dry; after grinding and cross 200 mesh sieves, under argon shield, 1100 ℃ of heat treatment 1 hour; with the stove cooling, obtain negative electrode active material A2.
The preparation of cathode pole piece
With 85 gram negative electrode active material A2 of preparation, carbon black 5 grams, carboxymethyl cellulose (CMC) 12 grams join in 900 milliliters of the deionized waters, stir in de-airing mixer then and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, 100 ℃ of following oven dry, roll-ins then, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated the copper film of about 300 nanometers respectively on its two sides by the PVD method, plated the two sides, back and become bronzing, the actual two sides of silicon active material all is wrapped in by copper film in the pole piece of preparation.
The preparation of anode pole piece
100 gram lithium cobalt oxygen, 3 gram binding agent Kynoar and 2 gram conductive agent acetylene blacks are joined in the 50 gram N-methyl pyrrolidones, and de-airing mixer stirs and forms uniform anode sizing agent then.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, 150 ℃ of oven dry, roll-ins then, is sliced into 480 * 44 millimeters positive pole, wherein contain the lithium cobalt oxygen active substances of 8 grams of having an appointment.
The battery equipment
Respectively with the electric core of positive pole, negative pole and a square lithium ion battery of membrane coil coiled of above-mentioned battery, subsequently lithium hexafluoro phosphate is dissolved in by the concentration of 1 mol in the mixed solvent of ethylene carbonate (EC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)=1: 1: 1 and forms nonaqueous electrolytic solution, about 3.5 grams of reservoir quantity in each battery, lithium rechargeable battery E2 is made in sealing.
Embodiment 3
(1) preparation of negative electrode active material
80 gram silica flours (average diameter is 10 microns) are mixed with 10 gram zinc powders (average diameter is 10 microns), pour 200 ml ethanols into, with 250 rev/mins rotating speeds ball milling 24 hours in ball mill (Zhengzhou City prosperous extra large machine-building Co., Ltd), take out oven dry, then, with the material after the oven dry under argon shield, 1300 ℃ of heat treatment 8.5 hours, take out with stove cooling back and to grind, cross 200 mesh sieves, make silicon the active metal complex;
Take by weighing 60 gram copper chlorides, be mixed with saturated solution, then with its with silicon the active metal complex mix, and stirred 1 hour, obtain turbid liquid;
The dilute hydrochloric acid solution that in above-mentioned solution, slowly adds 100 milliliter of 0.1 mol then, turbid liquid pH value is controlled at 4, and suction filtration then is after washed with de-ionized water 3～5 times, take out oven dry, obtain negative-electrode active material for secondary battery A3 by method preparation provided by the present invention.
The preparation of cathode pole piece
With the negative electrode active material A3 of preparation, 85 grams, carbon black 5 gram, carboxymethyl cellulose (CMC) 12 grams join in 900 milliliters of the deionized waters, stir in de-airing mixer then and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, 100 ℃ of following oven dry, roll-ins then, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated the copper film of about 300 nanometers respectively on its two sides by the PVD method, plated the two sides, back and become bronzing, the actual two sides of silicon active material all is wrapped in by copper film in the pole piece of preparation.
The preparation of anode pole piece
100 gram lithium cobalt oxygen, 3 gram binding agent Kynoar and 2 gram conductive agent acetylene blacks are joined in the 50 gram N-methyl pyrrolidones, and de-airing mixer stirs and forms uniform anode sizing agent then.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, 150 ℃ of oven dry, roll-ins then, is sliced into 480 * 44 millimeters positive pole, wherein contain the lithium cobalt oxygen active substances of 8 grams of having an appointment.
The battery equipment
Respectively with the electric core of positive pole, negative pole and a square lithium ion battery of membrane coil coiled of above-mentioned battery, subsequently lithium hexafluoro phosphate is dissolved in by the concentration of 1 mol in the mixed solvent of ethylene carbonate (EC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)=1: 1: 1 and forms nonaqueous electrolytic solution, about 3.5 grams of reservoir quantity in each battery, lithium rechargeable battery E3 is made in sealing.
Embodiment 4
(1) preparation of negative electrode active material
95 gram silica flours are mixed with 10 gram aluminium powders, add 200 ml ethanols simultaneously, with 250 rev/mins rotating speed ball millings 24 hours, take out oven dry then, under argon shield, 800 ℃ of heating 9 hours grind with stove cooling back taking-up with the material after the oven dry, 200 mesh sieves;
Take by weighing 105 gram cupric sulfate pentahydrate solids, be mixed with saturated solution, the material after just sieving then joins in the copper sulphate saturated solution, treats that all adding the back stirred 1 hour, makes sufficient reacting carry out, and obtains turbid liquid;
The dilute acetic acid solution that in above-mentioned turbid liquid, slowly adds 100 milliliter of 0.1 mol; turbid liquid pH is adjusted to 6; stop to stir after continuing to stir half an hour, suction filtration, and with after the washed with de-ionized water 3～5 times; take out oven dry; after grinding and cross 200 mesh sieves, under argon shield, 1100 ℃ of heat treatment 1 hour; with the stove cooling, obtain negative electrode active material A4.
The preparation of cathode pole piece
With 85 gram negative electrode active material A4 of preparation, carbon black 5 grams, carboxymethyl cellulose (CMC) 12 grams join in 900 milliliters of the deionized waters, stir in de-airing mixer then and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, 100 ℃ of following oven dry, roll-ins then, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated the copper film of about 300 nanometers respectively on its two sides by the PVD method, plated the two sides, back and become bronzing, the actual two sides of silicon active material all is wrapped in by copper film in the pole piece of preparation.
The preparation of anode pole piece
100 gram lithium cobalt oxygen, 3 gram binding agent Kynoar and 2 gram conductive agent acetylene blacks are joined in the 50 gram N-methyl pyrrolidones, and de-airing mixer stirs and forms uniform anode sizing agent then.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, 150 ℃ of oven dry, roll-ins then, is sliced into 480 * 44 millimeters positive pole, wherein contain the lithium cobalt oxygen active substances of 8 grams of having an appointment.
The battery equipment
Respectively with the electric core of positive pole, negative pole and a square lithium ion battery of membrane coil coiled of above-mentioned battery, subsequently lithium hexafluoro phosphate is dissolved in by the concentration of 1 mol in the mixed solvent of ethylene carbonate (EC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)=1: 1: 1 and forms nonaqueous electrolytic solution, about 3.5 grams of reservoir quantity in each battery, lithium rechargeable battery E4 is made in sealing.
Embodiment 5-8
Present embodiment is used for every performance of battery sample of test implementation example 1-4 preparation
Battery testing
The E1-E4 battery is placed on test cashier's office in a shop, carries out constant current charge with the 200mA electric current, the charging upper voltage limit is 4.2V, again with the 200mA constant-current discharge to 3.0V, record related data and see Table 1.
Table 1
| Sequence number | Initial charge capacity (mAh) | Discharge capacity (mAh) first | First charge-discharge efficiency (%) | The 100th cyclic discharge capacity capacity (mAh) |
| E1 | 1236 | 996 | 80.6 | 738 |
| E2 | 1256 | 1164 | 92.7 | 786 |
| E3 | 1220 | 1068 | 87.5 | 736 |
| E4 | 1248 | 1154 | 92.4 | 780 |
This shows that the negative electrode active material by method preparation provided by the present invention prepares the conductivity height, Stability Analysis of Structures, specific capacity height, good cycle, and negative electrode active material preparation method provided by the present invention, it is simple also to have technology, the advantage that trash discharge is few.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the preparation method of a lithium ion battery negative pole active materials, this method comprises:
1) silica flour is mixed with the active metal powder, and under the protective gas condition, heats, make the fusing of active metal powder, and be coated on silicon powder surface, obtain silicon the active metal complex;
2) with prepared silicon in the step (1) active metal complex fragmentation, after sieving, add the aqueous solution of mantoquita, redox reaction takes place, obtain turbid liquid;
3) add acetic acid or hydrochloric acid in the turbid liquid in step (2), pH is adjusted to 4-6, after filtration and the drying, obtain negative-electrode active material for secondary battery then; Described active metal is zinc or aluminium.
2. the weight ratio of silica flour and active metal powder is 7-9.5 among the preparation method of negative electrode active material according to claim 1, described step (1): 1.
3. the preparation method of negative electrode active material according to claim 1, the average diameter of the silica flour in the described step (1) is 0.01 micron-10 microns, active metal powder average diameter is 1 micron-10 microns.
4. the preparation method of negative electrode active material according to claim 1, the aqueous solution of the mantoquita in the described step (2) is selected from copper sulfate solution or copper chloride solution.
5. the preparation method of negative electrode active material according to claim 1, the active metal in the step (1) is a zinc, and heating-up temperature is 400-1300 ℃, and be 0.5 hour-10 hours heating time.
6. the preparation method of negative electrode active material according to claim 1, the active metal in the step (1) is an aluminium, and heating-up temperature is 650-800 ℃, and be 0.5 hour-10 hours heating time.
7. copper salt solution is the mantoquita saturated aqueous solution among the preparation method of negative electrode active material according to claim 1, described step (2), silicon the weight ratio of active metal complex and mantoquita be 1-1.5: 1.
8. the preparation method of negative electrode active material according to claim 1, the protective gas in the described step (1) is selected from argon gas or hydrogen.
9. the preparation method of negative electrode active material according to claim 1, the sieve mesh of sieving in the described step (2) is 200 orders.
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