CN102208617B - 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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- 238000000034 method Methods 0.000 title claims abstract description 47
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 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
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- 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 66
- 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 32
- 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
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- 239000011149 active material Substances 0.000 claims description 9
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- 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
- 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
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
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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
- 239000000463 material Substances 0.000 description 22
- 229910052744 lithium Inorganic materials 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
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 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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- 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
- 229910019142 PO4 Inorganic materials 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
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- 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
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- 238000000227 grinding Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
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- 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
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- 238000005229 chemical vapour deposition Methods 0.000 description 3
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- 238000009938 salting Methods 0.000 description 3
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- 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
- 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
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- 229910052742 iron Inorganic materials 0.000 description 2
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- 238000007747 plating Methods 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
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
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- 150000003376 silicon Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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, the demand of the lithium ion battery high for specific energy, that cycle performance is good is very urgent.At present in the business-like lithium ion battery negative material mainly take graphite as main.Yet, although graphite can show good performance as lithium ion battery negative material, because the restriction (372 MAh/gs) of its theoretical specific capacity has limited the further raising of lithium ion battery specific energy.And silicon receives much attention because it has high theoretical lithium storage content (reaching 4000 MAh/gs).
Yet, although 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 be electrically contacted, thereby so that material loses is electroactive, 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, so that the SEI film of negative terminal surface destroyed repeatedly and form, from having accelerated 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 preferably chemical property as active material in initial several times circulation, but the carrying out along with circulation, agglomeration can occur in nano-silicon, thereby capacity attenuation is very fast in follow-up cyclic process, and adopt nano-silicon expensive as negative material, even if the cycle performance in the time of improving it as negative pole, the possibility of large-scale commercial applications is also little.
Amorphous silicon can show good cyclical stability and very high reversible specific capacity (reaching more than 1000 MAh/gs), but its preparation method is difficult.Mainly be to deposit the unbodied silicon thin film of one deck by the method that adopts physical chemistry vapour deposition (PVD) or chemical vapour deposition (CVD) (CVD) at collection liquid surface at present.Because the silica-base material of this method preparation can show good chemical property 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 thinner 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 so that the reversible capacity that the collector on the unit are can provide is still very little, can't be applied to reality at all.
There is the people by ball grinding method that active metal and silicon is compound in the prior art, preparation negative electrode for lithium ion battery 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 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 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.The method adopts simple chemical combination method to be prepared from, in the metal of employing such as aluminium etc., in lithium intercalation can and electrolyte generation negative reaction, can reduce to a certain extent the cycle performance of material.
Summary of the invention
The present invention is complicated for solving in the prior art cathode material preparation method, and the technical problem that the negative material cyclical stability is low, irreversible capacity is large of preparation provides a kind of preparation method of lithium ion battery negative material, and the 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 the active metal complex broken, after sieving, add in the aqueous solution of mantoquita, redox reaction occurs, obtain turbid liquid;
3) add acetic acid or hydrochloric acid in the turbid liquid in the step 2, pH is adjusted to 4-6, then after suction filtration and the oven dry, obtain the secondary battery cathode material; 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 specific capacity is high, and good cycle, and negative electrode active material preparation method provided by the present invention also have the simple advantage of technique.
Embodiment
A kind of lithium ion battery silicium cathode material preparation method is provided among the present invention
The method specifically comprises:
1) silica flour is mixed with the 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 the active metal complex broken, after sieving, add the aqueous solution of mantoquita, redox reaction occurs, obtain turbid liquid;
3) add acetic acid or hydrochloric acid in the turbid liquid in the step 2, pH is adjusted to 4-6, then after suction filtration and the oven dry, obtain negative-electrode active material for secondary battery;
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 great many 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 large as lithium ion battery negative material in the prior art, the defective that cycle performance is poor, mainly be because, the huge change in volume in doff lithium process first of disclosed negative electrode active material in the prior art, so 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, namely produced a large amount of first irreversible capacities; Simultaneously because silicon volume in follow-up doff lithium cyclic process expands repeatedly and contraction so that pole piece top layer SEI film is destroyed, thereby electrolyte can be penetrated into active material inside, various side reactions constantly occurs, so that the non-constant of the 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 repeatedly expansion of silicon and be not destroyed, will set up on the other hand a stable SEI film system, the various side reactions that the infiltration of prevention electrolyte causes, the cycle performance of raising pole piece.By adopting the metallic copper to the lithium inertia to come the coated Si powder, can improve the conductivity of material, stop the negative reaction of silicon and electrolyte, simultaneously because metallic copper has good ductility, so that silicon is in the doff lithium process repeatedly in the expansion process, copper still can be coated on silicon powder surface well, so that 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 first irreversible capacity 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, the SEI film of self-assembling formation can stably exist in circulation subsequently always in the initial charge process, 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 large 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 occurs, this layer product is first destroyed in circulation subsequently, then forms again again, and this vicious circle repeatedly is inevitable so that the non-constant of the cycle performance of silicium cathode pole piece.Yet, by at the good copper film of the uniform ductility of silicium cathode pole piece plated surface last layer, can ideally solve the poor problem of silicium cathode pole piece cycle performance.At first, copper film is inertia to electrolyte and lithium, other side reaction can not occur, and can stably exist always; Secondly, its good ductility can bear 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; Again, 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 be from the activity weak metal simple-substance of this lively type of salting liquid displacing of weak metal, the movable metallic sequence list is K Ca Na Mg Al Zn Fe Sn Pb H CuHg Ag Pt Au, for the present invention, the position can be come from the salting liquid displacing metallic copper of the copper of H back at the metal of H front, its principle mainly is that the active metal in the salting liquid of copper displacement reaction has occured, 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 great many of experiments, the inventor finds that zinc and aluminium are comparatively suitable.
In the step 2 will with the silicon of preparation in the step 1 the active metal complex broken, 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 provides 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 the particle of excessive particle diameter repeatedly expands in the doff lithium cyclic process and shrinks and causes easily particle cracked, and too small particles becomes 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 the 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 an amount of ethanol, and the weight ratio of the 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 excessively low 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 is the 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 is conducive to 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, all add complete rear continuation until copper salt solution and stirred 1 hour, active metal in the turbid liquid is fully reduced after, need to add acetic acid or hydrochloric acid the pH value of turbid liquid be controlled at 4-6.The acetic acid of preferred 0.1 mol/L 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 the 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 the known film-making of oar technique slurry and the compressing tablet of drawing in the industry; The pole piece for preparing needs further copper plating film to process, and the coating process that adopts can adopt the known plating of industry or PVD technique, and preferred PVD technique because the concrete manufacture craft of above-mentioned negative plate is technique 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, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit 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, grind with taking out after the stove cooling, 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;
Then the dilute hydrochloric acid solution that slowly adds 100 milliliter of 0.1 mol/L in the mentioned solution, 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 the 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, then stir in de-airing mixer and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, then 100 ℃ of lower oven dry, roll-ins, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated respectively the copper film of about 300 nanometers on its two sides by the PVD method, plated rear two sides 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 1-METHYLPYRROLIDONEs, and then de-airing mixer stirs and forms uniform anode sizing agent.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, then 150 ℃ of oven dry, roll-ins, 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 battery 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/L 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 simultaneously 200 ml ethanols, 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 taking-up after the stove cooling 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 then just sieving joins in the copper sulphate saturated solution, stirs 1 hour after all adding, so that sufficient reacting carries out, obtains turbid liquid;
The dilute acetic acid solution that slowly adds 100 milliliter of 0.1 mol/L in the above-mentioned turbid liquid; 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, then stir in de-airing mixer and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, then 100 ℃ of lower oven dry, roll-ins, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated respectively the copper film of about 300 nanometers on its two sides by the PVD method, plated rear two sides 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 1-METHYLPYRROLIDONEs, and then de-airing mixer stirs and forms uniform anode sizing agent.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, then 150 ℃ of oven dry, roll-ins, 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 battery 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/L 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, grind with taking out after the stove cooling, 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;
Then the dilute hydrochloric acid solution that slowly adds 100 milliliter of 0.1 mol/L in the mentioned solution, 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 the 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, then stir in de-airing mixer and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, then 100 ℃ of lower oven dry, roll-ins, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated respectively the copper film of about 300 nanometers on its two sides by the PVD method, plated rear two sides 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 1-METHYLPYRROLIDONEs, and then de-airing mixer stirs and forms uniform anode sizing agent.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, then 150 ℃ of oven dry, roll-ins, 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 battery 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/L 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 simultaneously 200 ml ethanols, 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 taking-up after the stove cooling 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 then just sieving joins in the copper sulphate saturated solution, stirs 1 hour after all adding, so that sufficient reacting carries out, obtains turbid liquid;
The dilute acetic acid solution that slowly adds 100 milliliter of 0.1 mol/L in the above-mentioned turbid liquid; 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, then stir in de-airing mixer and form uniform cathode size.
It is 12 microns Copper Foil both sides that this cathode size is coated on thickness equably, then 100 ℃ of lower oven dry, roll-ins, cut to make and be of a size of 475 * 45 millimeters negative pole, the cathode pole piece of preparation is plated respectively the copper film of about 300 nanometers on its two sides by the PVD method, plated rear two sides 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 1-METHYLPYRROLIDONEs, and then de-airing mixer stirs and forms uniform anode sizing agent.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, then 150 ℃ of oven dry, roll-ins, 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 battery 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/L 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 the properties 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, charging upper limit voltage 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 is high, good cycle, and negative electrode active material preparation method provided by the present invention, it is simple also to have technique, the advantage that trash discharge is few.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing 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 (8)
1. the preparation method of a lithium ion battery negative pole active materials, the 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) the active metal complex broken, after sieving, add the aqueous solution of mantoquita, redox reaction occurs, obtain turbid liquid;
3) add acetic acid or hydrochloric acid in the turbid liquid in the step (2), pH be adjusted to 4-6, then filter and drying after, obtain negative-electrode active material for secondary battery; Described active metal is zinc or aluminium;
Wherein, the weight ratio of silica flour and active metal powder is 7-9.5:1 in the described step (1); In the described step (2) silicon the weight ratio of active metal complex and mantoquita be 1-1.5:1.
2. 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.
3. 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.
4. the preparation method of negative electrode active material according to claim 1, the active metal in the step (1) is zinc, and heating-up temperature is 400-1300 ℃, and be 0.5 hour-10 hours heating time.
5. the preparation method of negative electrode active material according to claim 1, the active metal in the step (1) is aluminium, and heating-up temperature is 650-800 ℃, and be 0.5 hour-10 hours heating time.
6. 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).
7. 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.
8. 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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