CN102082263B - Method for preparing conductive carbon film-coated calcium or calcium-tin alloy serving as anode material of lithium battery - Google Patents
Method for preparing conductive carbon film-coated calcium or calcium-tin alloy serving as anode material of lithium battery Download PDFInfo
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- CN102082263B CN102082263B CN2011100003684A CN201110000368A CN102082263B CN 102082263 B CN102082263 B CN 102082263B CN 2011100003684 A CN2011100003684 A CN 2011100003684A CN 201110000368 A CN201110000368 A CN 201110000368A CN 102082263 B CN102082263 B CN 102082263B
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- 239000011575 calcium Substances 0.000 title claims abstract description 140
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 101
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 92
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- DPDORTBBLUCNJG-UHFFFAOYSA-N calcium tin Chemical compound [Ca].[Sn] DPDORTBBLUCNJG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000010405 anode material Substances 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 60
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 229910052786 argon Inorganic materials 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 5
- 229910004767 CaSn Inorganic materials 0.000 claims description 41
- 229910001416 lithium ion Inorganic materials 0.000 claims description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 30
- 238000003763 carbonization Methods 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000000956 alloy Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000006023 eutectic alloy Substances 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 15
- 238000003860 storage Methods 0.000 description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 8
- 230000005496 eutectics Effects 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- 229910014689 LiMnO Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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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 relates to a method for preparing an anode material of a lithium battery and aims to provide a method for preparing a conductive carbon film-coated calcium or calcium-tin alloy serving as the anode material of the lithium battery. The method comprises the following steps of: melting high-purity calcium metal or calcium metal and tin metal, spraying into polyethylene glycol liquid byusing high purity argon, and cooling fog drops in the polyethylene glycol liquid to obtain spherical powder; carbonizing polyethylene glycol to obtain a carbon coated calcium material; filtering out the carbon coated calcium material; calcining again in vacuum or high purity nitrogen atmosphere at the temperature of below 700 DEG C; further carbonizing to remove residual polyethylene glycol on the carbon coated calcium material; and cooling to obtain the conductive carbon film-coated calcium serving as the anode material for preparing the lithium battery. A conductive carbon film is formed onthe surfaces of the calcium or calcium-tin alloy particles and is favorable for the stability of an electrode structure. A gas spraying method for preparing the carbon coated material is favorable for scale production and cost reduction.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, particularly conductive carbon film coats the preparation method of calcium or calcium tin material.
Background technology
Lightweight, the advantages such as capacity large, memory-less effect that lithium ion battery has, thereby obtained generally using.Present many digital equipments have all adopted lithium ion battery to make power supply.The energy density of lithium ion battery is very high, and its capacity is 1.5～2 times with the Ni-MH battery of weight, and to have very low self-discharge rate, do not contain the advantages such as noxious substance be the major reason of its extensive use.The people such as Japanese Nagoura were developed into take petroleum coke as negative pole in 1990, with LiCoO
2Lithium ion battery for positive pole: LiC
6| LiClO
4-PC+EC|LiCoO
2The same year.Moli and sony two macrocell companies declare will the lithium ion battery of release take carbon as negative pole.1991, Sony energy technology company and battery section developed jointly a kind of lithium ion battery take glycan alcohol RESEARCH OF PYROCARBON (PFA) as negative pole.Lithium ion battery negative material has graphite (C
6), sulfide: TiS
2, NbS
2, oxide: WO
3, V
2O
5, SnO
2Deng.Take graphite cathode material as example, negative reaction in the charge and discharge process:
C
6＋xLi
＋+?xe?==?Li
xC
6
When battery is charged, there is lithium ion to generate on the positive pole of battery, the lithium ion of generation arrives negative pole through electrolyte movement.And be layer structure as the graphite of negative pole, and it has a lot of micropores, and the lithium ion that arrives negative pole just is embedded in the micropore of carbon-coating, forms lithium intercalation compound (Li
xC
6), the lithium ion of embedding is more, and charging capacity is higher.When battery was discharged, the lithium ion that is embedded in the graphite linings was deviate from, and positive pole is got back in motion again.It is more to get back to anodal lithium ion, and discharge capacity is higher.
Negative material as lithium battery must be to possess following requirement: (1) lithium storage capacity is high; (2) embedding of lithium in negative material, to take off the embedding reaction fast, and namely the diffusion coefficient of lithium ion in solid phase is large, and be little in the mobile impedance at electrode-electric solution liquid interface; (3) existence of lithium ion in electrode material is stable; (4) in the charge and discharge cycles of battery, the negative material change in volume is little; (5) electron conduction is high; (6) negative material does not dissolve in electrolyte.
The selection of negative material has a great impact the performance of battery.At present cathode of lithium battery research and development mainly concentrates on material with carbon element and has the metal oxide of special construction.The most frequently used is graphite electrode, because graphitic conductive is good, degree of crystallinity is higher, has good layer structure, is fit to the embedding of lithium-take off embedding.And its slotting lithium current potential is low and smooth, can be lithium ion battery high stably operating voltage is provided, and is roughly: (vs. Li between 0.00～0.20 V
+/ Li).Japanese honda company utilizes poly-phenylene vinylene (ppv), and (the thermal decomposition product PPP-700(of Polyparaphenylene-PPP) is with PPP to 700 ℃ of certain firing rate heating, and the thermal decomposition product that obtains of insulation certain hour) as negative pole, reversible capacity can surpass LiC
6(372 mAh g
-1).
Metal oxide, its specific energy improves greatly than carbon negative pole material.Such as SnO
2, WO
2, MoO
2, VO
2, TiO
2, Li
xFe
2O
3, Li
4Ti
5O
12, Li
4Mn
5O
12Deng, but conductivity is not as graphite electrode usually, and the high power discharge performance of the lithium ion battery take metal oxide as negative pole is relatively poor.The reversible high Storage mechanism of lithium in graphite material mainly contains lithium dimer Li
2Form mechanism, multilayer lithium mechanism, lattice dot matrix mechanism, elastic ball-elastic network(s) model, layer-Bian end-surface storage lithium mechanism, nanoscale graphite storage lithium mechanism, carbon-lithium-hydrogen mechanism and micropore storage lithium mechanism.
Metallic tin can form up to Li with Li
4.4The alloy of Sn has very high theoretical specific capacity (992 mAh g
-1), but Li and Sn are accompanied by huge volumetric expansion when forming alloy, and cycle performance is poor.Have result of study to show, reserve the electrode structure of cavity, the Sn nano particle is filled in the flexible carbon hollow ball, preparation carbon-coated nano tin is so that the Li after the embedding Li volumetric expansion
4.4The Sn alloy also can be accommodated in the carbon hollow ball, thereby has eliminated Li insertion/deviate from the stress that produces in the process, has greatly improved the cycle performance of electrode material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of conductive carbon film than material with carbon element and Xi Geng height ratio capacity to coat calcium or calcium ashbury metal nano material and preparation method thereof.
Be the technical solution problem, concrete scheme of the present invention is:
Provide a kind of conductive carbon film to coat the lithium cell cathode material preparation method of calcium or calcium ashbury metal, the steps include:
(1) gets after purity is the fusing of 99.99% calcium metal, with the high-purity argon spraying of purity 99.999%, be ejected into molecular weight and be 200 ~ 800, purity is in 99% the polyethylene glycol liquid, formation spherical powder after the calcium droplet cool off in polyethylene glycol liquid; Meanwhile, the polyethylene glycol generation carbonization that contacts with the calcium droplet, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats calcium material;
(2) filter out carbon and coat calcium material, again calcining in the atmosphere of the high-purity argon of vacuum or purity 99.999%, temperature is controlled at 700
oBelow the C, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material; After the cooling, namely obtain coating calcium as the conductive carbon film of preparation lithium ion battery negative material.
The present invention also provides a kind of conductive carbon film to coat the lithium cell cathode material preparation method of calcium ashbury metal, the steps include:
(1) getting purity is that 99.99% calcium metal and tin are 250 ~ 1200
oAfter the C fusing, with the high-purity argon spraying of purity 99.999%, be ejected into molecular weight and be 200 ~ 800, purity is in 99% the polyethylene glycol liquid, formation spherical powder after calcium ashbury metal droplet cool off in polyethylene glycol liquid; Meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats the calcium tin alloy material;
(2) filter out carbon and coat the calcium tin alloy material, again calcining in the atmosphere of the high-purity argon of vacuum or purity 99.999%, temperature is controlled at 700
oBelow the C, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium tin alloy material; After the cooling, namely obtain coating the calcium ashbury metal as the carbon of preparation lithium ion battery negative material.
Among the present invention, described calcium ashbury metal is with general formula Ca
xSn
yExpression, wherein: 0 ﹤ x≤2,0 ﹤ y≤3.
Among the present invention, described calcium ashbury metal is any one in the following alloy form: Ca-Ca
2Sn eutectic alloy, CaSn-CaSn
3Eutectic alloy, Ca
2The Peritectic Alloy that Sn and CaSn form, CaSn
3With the alloy of Sn formation, or intermetallic compound Ca
2Sn, CaSn, CaSn
3
The present invention further provides a kind of lithium battery that uses aforementioned negative material preparation, the electrolyte of this lithium battery is with LiPF
6Be solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, the LiPF in the electrolyte
6Concentration be 1 mol L
-1This lithium battery is take microporous polypropylene membrane as barrier film, with LiCoO
2, LiMnO
2Or LiFePO
4Be positive electrode.
Among the present invention, described positive pole prepares by following method: anode material for lithium-ion batteries LiCoO
2, LiMnO
2Or LiFePO
4: acetylene black: polyacrylic acid solution (5wt%) is 95: 5: 5 ~ 20 in mass ratio, and mechanical mixture 10 ~ 30 minutes is modulated into paste, is coated on the carbon paper, dries in the shade; At 20 ~ 100 Kg cm
-2Pressure under compressing.
Among the present invention with calcium metal as lithium cell cathode material, be can form alloy Li with lithium according to calcium
2Ca realizes that lithium storage content is up to 1340 mAh g
-1, calcium metal generation embedding lithium and take off lithium reaction in the charge and discharge process:
Ca＋2Li
＋+?2e?==?Li
2Ca
The face-centered cubic lattice of calcium metal changes Li into
2The hexagonal lattice of Ca, unit cell volume obviously expands, and forms very large stress, hinders proceeding of embedding lithium reaction.Therefore pure calcium is as the negative material of lithium battery, although theoretical capacity is very high, actual being difficult to reaches, and because the stress that the embedding lithium produces is very large, causes charging voltage higher, causes easily the decomposition of electrolyte.
Among the present invention with the calcium ashbury metal as lithium cell cathode material, be according to elemental metals calcium and tin and intermetallic compound Ca
2Sn, CaSn, CaSn
3Can both store up that the characteristic of lithium realizes.By Ca
2Sn, CaSn and CaSn
3Can form respectively Li
8Ca
2Sn, Li
6CaSn and Li
14CaSn
3, their lithium storage content can reach respectively 1079 mAh g
-1, 1013 mAh g
-1With 947 mAh g
-1
Among the present invention, the eutectic structure that described calcium ashbury metal forms can significantly reduce charging voltage, increases substantially high-rate charge-discharge capability.Its flourishing eutectic structure that has its source in, the particle of remarkable refinement elemental metals or intermetallic compound, flourishing intergranular layer not only provides unobstructed lithium diffusion admittance, and the lithium storage content of intergranular layer will be higher than the lithium storage content of crystal grain inside.
Among the present invention, the calcium that conductive carbon film coats or calcium ashbury metal are as the negative material of lithium ion battery, because calcium or calcium ashbury metal particle are among the coating of conductive carbon film, the lithium ion battery change in volume that the taking off of lithium ion/embedding causes in calcium or the calcium ashbury metal in charge and discharge process all coats in the capsule at conductive carbon film and occurs, can not cause coming off of negative material, stablize the structure of negative pole, thereby improve the life-span of lithium ion battery.This point is showing particularly outstandingly aspect the high power charging-discharging cycle life that improves lithium ion battery.
The beneficial effect that the present invention has:
The present invention utilizes calcium to have the characteristic of high storage lithium specific capacity, forms a kind of lithium ion battery negative material of high power capacity.Utilize calcium constituent can form with tin the characteristic of intermetallic compound, form the crystal grain with eutectic feature, the intergranular layer that forms between elemental metals or the intermetallic compound provides spacious lithium diffusion admittance.Be conducive to the stable of electrode structure at calcium or calcium ashbury metal particle surface formation conductive carbon film.Adopting gas atomization to prepare carbon encapsulated material is conducive to large-scale production and reduces cost.Carbon of the present invention coat the calcium tin alloy material have (1) stably the charging/discharging voltage platform make organic bath safer in battery applications; (2) good electrode reaction invertibity; (3) good chemical stability and thermal stability; (4) cheap and be easy to preparation; (5) pollution-free; Safer when (6) processing with operation.The conductive carbon film that adopts spraying to send out preparation has even thickness, the advantage of good conductivity, thus the electrochemical kinetics performance of raising negative pole reduces electrode polarization, improves the speed capabilities of lithium battery, can be applicable to the electrokinetic cell of electric automobile.
Description of drawings
Fig. 1 is that the carbon of embodiment two preparations coats Ca-Ca
2The metallographic of Sn eutectic alloy charge and discharge process changes.
Fig. 2 is that the carbon of embodiment three preparations coats CaSn-CaSn
3The eutectic alloy charging and discharging curve.
Reference numeral among Fig. 1 is: (101) carbon film, (102) calcium, (103) calcium two tin (Ca
2Sn), (104) Ca-Ca
2Sn eutectic grain, (105) Li
2Ca, (106) Li
8Ca
2Sn, (107) Li
8Ca
2Sn and Li
2The layer structure of Ca.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment one: carbon coats the calcium material preparation
Get purity and be 99.99% granules of metal Ca and be heated to 850
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical powder after the calcium droplet cools off in polyethylene glycol liquid, meanwhile, the polyethylene glycol generation carbonization that contacts with the calcium droplet forms carbon and coats calcium material.The molecular weight of polyethylene glycol is 800, and purity is 99%.
Filter out carbon and coat calcium material, again calcining in the atmosphere of vacuum, temperature is controlled at 600
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat calcium material as the negative material of high-capacity lithium ion cell.
Embodiment two: carbon coats Ca-Ca
2The preparation of Sn eutectic alloy
Get purity and be in mass ratio 58:42 of 99.99% calcium metal and tin grain, 900
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical Ca-Ca after calcium ashbury metal droplet cools off in polyethylene glycol liquid
2The Sn eutectic powder, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats Ca-Ca
2The Sn eutectic material.The molecular weight of polyethylene glycol is 600, and purity is 99%.Filter out carbon and coat Ca-Ca
2The Sn eutectic material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 700
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat Ca-Ca
2The Sn eutectic material is as the negative material of high-capacity lithium ion cell.Fig. 1 is that carbon coats Ca-Ca
2The metallographic of Sn eutectic alloy charge and discharge process changes.
Embodiment three: carbon coats CaSn-CaSn
3The eutectic alloy preparation
Get purity and be in mass ratio 13.5:86.5 of 99.99% calcium metal and tin grain, 700
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical CaSn-CaSn after calcium ashbury metal droplet cools off in polyethylene glycol liquid
3Eutectic powder, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats CaSn-CaSn
3Eutectic material.The molecular weight of polyethylene glycol is 200, and purity is 99%.Filter out carbon and coat CaSn-CaSn
3Eutectic material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 550
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat CaSn-CaSn
3Eutectic material is as the negative material of high-capacity lithium ion cell.Its charge-discharge performance as shown in Figure 2.Electrolyte adopts with LiPF
6Be solute, ethylene carbonate (EC), methyl carbonate (MC) are solvent with the mixture of dimethyl carbonate (DMC), and the mass ratio of ethylene carbonate, methyl carbonate and dimethyl carbonate is EC:MC:DMC=4:2:4.LiPF
6Concentration be 1 mol L
-1
Embodiment four: carbon coats Ca
2The preparation of Sn-CaSn Peritectic Alloy
Get purity and be in mass ratio 30:70 of 99.99% calcium metal and tin grain, 1200
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical Ca after calcium ashbury metal droplet cools off in polyethylene glycol liquid
2Sn-CaSn peritectoid powder, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats Ca
2Sn-CaSn peritectoid material.The molecular weight of polyethylene glycol is 400, and purity is 99%.Filter out carbon and coat Ca
2Sn-CaSn peritectoid material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 700
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat Ca
2Sn-CaSn peritectoid material is as the negative material of high-capacity lithium ion cell.
Embodiment five: Compound C a between carbon-clad metal
2The preparation of Sn
Get purity and be in mass ratio 40:60 of 99.99% calcium metal and tin grain, 1200
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical Ca after calcium ashbury metal droplet cools off in polyethylene glycol liquid
2The Sn powder, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats Ca
2The Sn material.The molecular weight of polyethylene glycol is 800, and purity is 99%.Filter out carbon and coat Ca
2The Sn material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 700
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat Ca
2The Sn material is as the negative material of high-capacity lithium ion cell.
Embodiment six: the preparation of Compound C aSn between carbon-clad metal
Get purity and be in mass ratio 33:67 of 99.99% calcium metal and tin grain, 1100
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, after cooling off, calcium ashbury metal droplet forms spherical CaSn powder in polyethylene glycol liquid, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats the CaSn material.The molecular weight of polyethylene glycol is 800, and purity is 99%.Filter out carbon and coat the CaSn material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 700
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat the CaSn material as the negative material of high-capacity lithium ion cell.
Embodiment seven: Compound C aSn between carbon-clad metal
3Preparation
Get purity and be in mass ratio 10:90 of 99.99% calcium metal and tin grain, 650
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical CaSn after calcium ashbury metal droplet cools off in polyethylene glycol liquid
3Powder, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats the CaSn material.The molecular weight of polyethylene glycol is 400, and purity is 99%.Filter out carbon and coat CaSn
3Material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 600
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat CaSn
3Material is as the negative material of high-capacity lithium ion cell.
Embodiment eight: carbon coats CaSn
3-Sn alloy is the lithium battery of negative pole
Get purity and be in mass ratio 5:95 of 99.99% calcium metal and tin grain, 630
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, form spherical CaSn after calcium ashbury metal droplet cools off in polyethylene glycol liquid
3-Sn alloy powder, meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet forms carbon and coats CaSn
3-Sn alloy material.The molecular weight of polyethylene glycol is 200, and purity is 99%.Filter out carbon and coat CaSn
3-Sn alloy material, again calcining in the atmosphere of high-purity argon (purity 99.999%), temperature is controlled at 550
oC, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material.After the cooling, obtain carbon and coat CaSn
3-Sn alloy material is as the negative material of lithium ion battery.
With above-mentioned negative material and acetylene black: polyacrylic acid solution (5wt%) is 95: 5: 5 in mass ratio, and mechanical mixture 30 minutes is modulated into paste, is coated on the aluminium film, dries in the shade; At 100 Kg cm
-2Pressure under compressing, obtain negative pole.
With anode material for lithium-ion batteries LiCoO
2, LiMnO
2Or LiFePO
4: acetylene black: polyacrylic acid solution (5wt%) is 95: 5: 5 in mass ratio, and mechanical mixture 30 minutes is modulated into paste, is coated on the aluminium film, dries in the shade; At 100 Kg cm
-2Pressure under compressing, can obtain respectively LiCoO
2Anodal, LiMnO
2Positive pole and LiFePO
4Anodal.
The employing microporous polypropylene membrane is barrier film.The electrode material side of anodal and negative pole is formed sandwich structure with barrier film in opposite directions, inject electrolyte.Can obtain respectively coating CaSn with carbon
3-Sn alloy is negative material, with LiCoO
2, LiMnO
2And LiFePO
4Three kinds of lithium batteries for positive pole.Electrolyte is with LiPF
6Be solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, the LiPF in the electrolyte
6Concentration be 1 mol L
-1
What more than announce at last, only is specific embodiments of the invention.Ca among the present invention and Ca
xSn
yAlloy is as negative material, all can with LiCoO
2, LiMnO
2Or LiFePO
4The positive electrode pairing consists of lithium battery.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. conductive carbon film coats the preparation method of the lithium cell cathode material of calcium, the steps include:
(1) gets after purity is the fusing of 99.99% calcium metal, with the high-purity argon spraying of purity 99.999%, be ejected into molecular weight and be 200～800, purity is in 99% the polyethylene glycol liquid, formation spherical powder after the calcium droplet cool off in polyethylene glycol liquid; Meanwhile, the polyethylene glycol generation carbonization that contacts with the calcium droplet, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats calcium material;
(2) filter out carbon and coat calcium material, again calcining in the atmosphere of the high-purity argon of vacuum or purity 99.999%, temperature is controlled at 700
oBelow the C, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium material; After the cooling, namely obtain coating calcium as the conductive carbon film of preparation lithium ion battery negative material.
2. conductive carbon film coats the preparation method of the lithium cell cathode material of calcium ashbury metal, the steps include:
(1) getting purity is that 99.99% calcium metal and tin are 250～1200
oAfter the C fusing, with the high-purity argon spraying of purity 99.999%, be ejected into molecular weight and be 200～800, purity is in 99% the polyethylene glycol liquid, formation spherical powder after calcium ashbury metal droplet cool off in polyethylene glycol liquid; Meanwhile, the polyethylene glycol generation carbonization that contacts with calcium ashbury metal droplet, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats the calcium tin alloy material;
(2) filter out carbon and coat the calcium tin alloy material, again calcining in the atmosphere of the high-purity argon of vacuum or purity 99.999%, temperature is controlled at 700
oBelow the C, further carbonization is to remove the polyethylene glycol that remains on the carbon coating calcium tin alloy material; After the cooling, namely obtain coating the calcium ashbury metal as the carbon of preparation lithium ion battery negative material.
3. method according to claim 2 is characterized in that, described calcium ashbury metal is with general formula Ca
xSn
yExpression, wherein: 0 ﹤ x≤2,0 ﹤ y≤3.
4. method according to claim 2 is characterized in that, described calcium ashbury metal is any one in the following alloy form: Ca-Ca
2Sn eutectic alloy, CaSn-CaSn
3Eutectic alloy, Ca
2Peritectic Alloy, CaSn that Sn and CaSn form
3Alloy or intermetallic compound Ca with Sn formation
2Sn, CaSn, CaSn
3
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Non-Patent Citations (4)
| Title |
|---|
| 任建国等.锂离子电池合金负极材料的研究进展.《化学进展》.2005,第17卷(第4期),第597页左栏第1段至第599页左栏第3段. |
| 任慢慢等.核壳结构的锂离子电池材料.《化学进展》.2008,第20卷(第5期),第771页右栏第1段至第772页左栏第1段，第773页右栏第2段至774页右栏第4段. |
| 核壳结构的锂离子电池材料;任慢慢等;《化学进展》;20080531;第20卷(第5期);第771页右栏第1段至第772页左栏第1段，第773页右栏第2段至774页右栏第4段 * |
| 锂离子电池合金负极材料的研究进展;任建国等;《化学进展》;20050731;第17卷(第4期);第597页左栏第1段至第599页左栏第3段 * |
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