CN102082263A - 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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- CN102082263A CN102082263A CN2011100003684A CN201110000368A CN102082263A CN 102082263 A CN102082263 A CN 102082263A CN 2011100003684 A CN2011100003684 A CN 2011100003684A CN 201110000368 A CN201110000368 A CN 201110000368A CN 102082263 A CN102082263 A CN 102082263A
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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 by using 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 on the 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
In light weight, advantages such as capacity big, memory-less effect that lithium ion battery has, thereby obtained widespread usage.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 advantages such as Toxic matter be the major reason of its extensive use.It is negative pole that people such as Japanese Nagoura in 1990 are developed into the petroleum coke, 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 that with releasing with carbon be the lithium ion battery of negative pole.1991, it was the lithium ion battery of negative pole with glycan alcohol RESEARCH OF PYROCARBON (PFA) that Sony energy technology company and battery portion have developed jointly a kind of.Lithium ion battery negative material has graphite (C
6), sulfide: TiS
2, NbS
2, oxide: WO
3, V
2O
5, SnO
2Deng.With the graphite cathode material is 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 many more, and charging capacity is high more.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 many more to get back to anodal lithium ion, and discharge capacity is high more.
Negative material as lithium battery must be to possess following requirement: (1) lithium storage capacity height; (2) embedding of lithium in negative material, to take off the embedding reaction fast, and promptly the diffusion coefficient of lithium ion in solid phase is big, and the mobile impedance of separating the liquid interface at electrode-electric is little; (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 height; (6) negative material does not dissolve in electrolyte.
The selection of negative material has very big influence to the performance of battery.Cathode of lithium battery research and development at present 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 operating voltage stably 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.As SnO
2, WO
2, MoO
2, VO
2, TiO
2, Li
xFe
2O
3, Li
4Ti
5O
12, Li
4Mn
5O
12Deng, but usually conductivity is that the high power discharge performance of lithium ion battery of negative pole is relatively poor with the metal oxide not as graphite electrode.Reversible high the store 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 makes 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 that the calcium droplet cool off back formation spherical powder in 99% the polyethylene glycol liquid 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, calcining once more 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, promptly 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,, be ejected into molecular weight and be 200 ~ 800 with the high-purity argon spraying of purity 99.999%, purity is that calcium ashbury metal droplet cool off back formation spherical powder in 99% the polyethylene glycol liquid 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, calcining once more 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, promptly 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, this electrolyte for Lithium Battery is with LiPF
6Be solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is a 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 a barrier film with the microporous polypropylene membrane, 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 by 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 compression moulding.
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 big stress, hinders proceeding of embedding lithium reaction.Therefore pure calcium is as the negative material of lithium battery, though theoretical capacity is very high, actual being difficult to reaches, and because the stress that the embedding lithium is produced is very big, causes charging voltage higher, causes the decomposition of electrolyte easily.
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 Li respectively
8Ca
2Sn, Li
6CaSn and Li
14CaSn
3, their lithium storage content can reach 1079 mAh g respectively
-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, 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 caused in calcium or the calcium ashbury metal in charge and discharge process all coats in the capsule at conductive carbon film and takes place, 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 the characteristic of intermetallic compound with tin, form the crystal grain with eutectic feature, the intergranular layer that forms between elemental metals or the intermetallic compound provides spacious lithium diffusion admittance.Help 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 helps 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) handling with operation.It is even that the conductive carbon film that adopts spraying to send out preparation has 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, the calcium droplet cools off the back and forms spherical powder in polyethylene glycol liquid, and 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, calcining once more 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 the negative material of calcium material as high-capacity lithium ion cell.
Embodiment two: carbon coats Ca-Ca
2The preparation of Sn eutectic alloy
Get purity and be 99.99% calcium metal and tin grain by mass ratio 58:42,900
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, calcium ashbury metal droplet cools off the back and forms spherical Ca-Ca 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, calcining once more 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 coats Ca-Ca for carbon
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 99.99% calcium metal and tin grain by mass ratio 13.5:86.5,700
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, calcium ashbury metal droplet cools off the back and forms spherical CaSn-CaSn 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, calcining once more 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 99.99% calcium metal and tin grain by mass ratio 30:70,1200
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, calcium ashbury metal droplet cools off the back and forms spherical Ca 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, calcining once more 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 99.99% calcium metal and tin grain by mass ratio 40:60,1200
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, calcium ashbury metal droplet cools off the back and forms spherical Ca 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, calcining once more 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 99.99% calcium metal and tin grain by mass ratio 33:67,1100
oAfter the C fusing,, be ejected in the polyethylene glycol liquid with high-purity argon (purity 99.999%) spraying, calcium ashbury metal droplet cools off the back and 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, calcining once more 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 negative material of CaSn material as high-capacity lithium ion cell.
Embodiment seven: Compound C aSn between carbon-clad metal
3Preparation
Get purity and be 99.99% calcium metal and tin grain by mass ratio 10:90,650
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, calcium ashbury metal droplet cools off the back and forms spherical CaSn 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, calcining once more 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 99.99% calcium metal and tin grain by mass ratio 5:95,630
oAfter the C fusing, with high-purity argon (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, calcium ashbury metal droplet cools off the back and forms spherical CaSn 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, calcining once more 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 by 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 compression moulding, 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 by 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 compression moulding, can obtain LiCoO respectively
2Anodal, LiMnO
2Positive pole and LiFePO
4Anodal.
The employing microporous polypropylene membrane is a 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 a 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 a 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 constitutes 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 (6)
1. conductive carbon film coats the preparation method of the lithium cell cathode material 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 that the calcium droplet cool off back formation spherical powder in 99% the polyethylene glycol liquid 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, calcining once more 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, promptly 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,, be ejected into molecular weight and be 200 ~ 800 with the high-purity argon spraying of purity 99.999%, purity is that calcium ashbury metal droplet cool off back formation spherical powder in 99% the polyethylene glycol liquid 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, calcining once more 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, promptly 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
2The Peritectic Alloy that Sn and CaSn form, CaSn
3With the alloy of Sn formation, or intermetallic compound Ca
2Sn, CaSn, CaSn
3
5. use the lithium battery of the preparation of negative material described in the claim 1 or 2, it is characterized in that this electrolyte for Lithium Battery is with LiPF
6Be solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is a 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 a barrier film with the microporous polypropylene membrane, with LiCoO
2, LiMnO
2Or LiFePO
4Be positive electrode.
6. lithium battery according to claim 5 is characterized in that described positive pole prepares by following method: with anode material for lithium-ion batteries LiCoO
2, LiMnO
2Or LiFePO
4: acetylene black: polyacrylic acid solution (5wt%) is 95: 5: 5 ~ 20 by 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 compression moulding.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104054210A (en) * | 2012-01-20 | 2014-09-17 | 株式会社丰田自动织机 | Secondary battery |
| CN104054210B (en) * | 2012-01-20 | 2016-04-27 | 株式会社丰田自动织机 | Secondary cell |
| US9444100B2 (en) | 2012-01-20 | 2016-09-13 | Kabushiki Kaisha Toyota Jidoshokki | Secondary battery |
| CN109888243A (en) * | 2019-03-13 | 2019-06-14 | 蒙娜丽莎集团股份有限公司 | A kind of preparation method of multistage composite metal oxide functional ceramics |
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