CN102082267B - Preparation and application of conductive carbon film-coated calcium nitride compound serving as anode material of lithium battery - Google Patents
Preparation and application of conductive carbon film-coated calcium nitride compound serving as anode material of lithium battery Download PDFInfo
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Abstract
The invention relates to preparation and application of an anode material of a lithium battery and aims to provide preparation and the application of a conductive carbon film-coated calcium nitride compound serving as the anode material of the lithium battery. The preparation method comprises the following steps of: after calcium metal is molten, spraying into polyethylene glycol liquid by using high purity nitrogen, and performing a reaction of the calcium fog drops and nitrogen in an nitriding atmosphere to obtain Ca3N2 microspheres so as to obtain a carbon-coated calcium nitride material primary product; and after filtering out a carbon-coated calcium nitride material, calcining for 2 to 3 hours again in the high purity nitrogen atmosphere and carrying out refining to obtain carbon-coated Ca3N2, or calcining for 2 to 3 hours again in vacuum to obtain a carbon-coated Ca3N2-Ca2N mixture. In the invention, a conductive carbon film is formed on the surface of Ca3N2 or Ca3N2-Ca2N, is favorable for stability of an electrode structure, has high heat stability and low cost, is easy to prepare and has no pollution. The conductive carbon film prepared by a spraying method has the advantages of uniform thickness and high conductivity. The electrode polarization is reduced. The speed and the capacity of the lithium battery are improved.
Description
Technical field
The present invention relates to a kind of preparation and application of lithium ion battery negative material, particularly conductive carbon film coats the lithium cell cathode material preparation method of nitrogen calcium compound, and the lithium ion battery that uses this negative material preparation.
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 nitrogen calcium compound has two kinds, i.e. Ca
2N and Ca
3N
2Ca
3N
2Be commonly called as and be CaCl2.The synthetic method of tradition CaCl2 is elemental metals calcium 450 ℃ of lower reactions 3～4 hours in nitrogen stream, and calcium metal changes body-centered cubic into by hexagonal, and it is loose that metal structure becomes, so nitridation reaction speed is very fast.Patent (CN03815383.1) discloses a kind of method for calcium nitride synthesis, and this synthesis technique comprises by means of an injector and being ejected in the reactor that comprises the nitrogen that is in high temperature with the zinc-calcium alloy of droplet form with melting.The CaCl2 that produces is collected in the collector unit of the bottom that is in reactor.The zinc that is contained in the droplet is evaporated, and condenses on the wall that is cooled of described reactor and is reused for preparation zinc-calcium alloy.
The electrode material that carbon encapsulated material is widely used in lithium battery synthesizes, such as the positive electrode of carbon-coated LiFePO 4 for lithium ion batteries and the negative material of carbon-coated nano tin.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.Carbon encapsulated material adds carbon source such as glucose, polyethylene glycol usually in electrode material is synthetic, at the calcination process of composite electrode material, glucose, polyethylene glycol decompose carbonization and obtain carbon encapsulated material.
Summary of the invention
The technical problem to be solved in the present invention is, provide a kind of than material with carbon element more the conductive carbon film of height ratio capacity coat the lithium cell cathode material preparation method of nitrogen calcium compound, and the lithium ion battery that uses this negative material preparation.
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 CaCl2, the steps include:
(1) gets after purity is the fusing of 99.99% calcium metal, with the High Purity Nitrogen spraying of purity 99.999%, be ejected into molecular weight and be 200 ~ 800, purity is that the calcium droplet generates Ca with the nitrogen reaction in 99% the polyethylene glycol liquid in blanket of nitrogen
3N
2Microballoon forms spherical powder after the cooling in polyethylene glycol liquid; Meanwhile, with Ca
3N
2The polyethylene glycol generation carbonization of contact, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats CaCl2 material primary product;
(2) filter out carbon and coat the CaCl2 material after, implement follow-up any treatment step:
In the atmosphere of the High Purity Nitrogen of purity 99.999%, again calcine and made with extra care in 2 ~ 3 hours, temperature is controlled at below 700 ℃, make carbon coat residual calcium and nitrogen reaction in the CaCl2 material, eliminate residual calcium, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating Ca as the carbon of preparation lithium ion battery negative material
3N
2Perhaps,
Again calcined in a vacuum 2 ~ 3 hours, temperature is controlled at below 700 ℃, makes carbon coat residual calcium and CaCl2 reaction in the CaCl2 material, generates Ca
2N, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating Ca as the carbon of preparation lithium ion battery negative material
3N
2-Ca
2The N mixture.
Among the present invention, prepare the method for cathode of lithium battery with aforementioned lithium cell cathode material, the steps include: carbon is coated Ca
3N
2Or carbon coats Ca
3N
2-Ca
2N mixture and polyacrylic acid ethanolic solution (5wt%) are 90: 10 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, namely obtain cathode of lithium battery.
Among the present invention, with the lithium battery of aforementioned negative material preparation, be take microporous polypropylene membrane as barrier film, electrode material side anodal and negative pole forms sandwich structure, built-in electrolyte with barrier film in opposite directions; It is characterized in that this lithium battery is with LiCo
(1-x)Mn
xO
2Or LiFePO
4Be positive electrode, wherein 0≤x≤1; 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
Among the present invention, the preparation process of the positive pole of lithium battery is:
LiCo in mass ratio
(1-x)Mn
xO
2Or LiFePO
4: acetylene black: polyacrylic acid ethanolic solution (5wt%) is 95: 5: 5, 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 LiCo
(1-x)Mn
xO
2Positive pole or LiFePO
4Anodal.
Among the present invention with Ca
3N
2And Ca
2N is as lithium cell cathode material, is can form respectively Li during according to this lithium cell charging
2Ca and LiCaN, lithium storage content are respectively 724 and 855 mAh g
-1, be higher than present business-like graphite cathode material.Ca in the charge and discharge process
3N
2And Ca
2The embedding lithium occurs and takes off the lithium reaction in N:
Ca
3N
2＋4Li
＋+?4e?==?Li
2Ca?+?2LiCaN
Ca
2N＋3Li
＋+?3e?==?Li
2Ca?+?LiCaN
Among the present invention, carbon coats Ca
3N
2Or carbon coats Ca
3N
2-Ca
2N is as the negative material of lithium ion battery, because these intercalation materials of li ions are among the coating of conductive carbon film, the efflorescence that electrode material that disproportionated reaction causes occurs in charging process these intercalation materials of li ions all is controlled at conductive carbon film and coats in the capsule and occur, 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 Ca
3N
2And Ca
2N has the characteristic of high storage lithium specific capacity, forms a kind of lithium ion battery negative material of high power capacity.At Ca
3N
2Ca
3N
2Or Ca
3N
2-Ca
2The N surface forms conductive carbon film and is conducive to the stable of electrode structure.Adopting gas atomization to prepare carbon encapsulated material is conducive to large-scale production and reduces cost.Carbon of the present invention coats Ca
3N
2Coat Ca with carbon
3N
2-Ca
2The N mixture material has good thermal stability; Cheap and be easy to preparation; Pollution-free.Adopt the conductive carbon film of spray-on process preparation to have 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 one preparation coats Ca
3N
2Charging and discharging curve.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment one: carbon coats Ca
3N
2Preparation
Get purity and be 99.99% granules of metal Ca and be heated to 850
oAfter the C fusing, with High Purity Nitrogen (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, the calcium droplet generates CaCl2 (Ca with the nitrogen reaction in blanket of nitrogen
3N
2) microballoon, be 200 at molecular weight, purity is to form spherical powder in 99% the polyethylene glycol liquid after the cooling; Meanwhile, the polyethylene glycol generation carbonization that contacts with CaCl2, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats CaCl2 material primary product.
Filter out carbon and coat Ca
3N
2Primary product is again calcined in the atmosphere of the High Purity Nitrogen of purity 99.999% and was made with extra care in 2 hours, and temperature is controlled at 700
oBelow the C, make carbon coat residual calcium and nitrogen reaction in the CaCl2 material, eliminate residual calcium, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating CaCl2 as the carbon of preparation lithium ion battery negative material.
Embodiment two: carbon coats Ca
3N
2Lithium battery (1) for negative pole
Get purity and be 99.99% calcium metal, 850
oAfter the C fusing, with High Purity Nitrogen (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, the calcium droplet generates CaCl2 (Ca with the nitrogen reaction in blanket of nitrogen
3N
2) microballoon, be 600 at molecular weight, purity is to form spherical powder in 99% the polyethylene glycol liquid after the cooling; Meanwhile, the polyethylene glycol generation carbonization that contacts with CaCl2, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats CaCl2 material primary product.
Filter out carbon and coat Ca
3N
2Primary product is again calcined in the atmosphere of the High Purity Nitrogen of purity 99.999% and was made with extra care in 3 hours, and temperature is controlled at 650
oBelow the C, make carbon coat residual calcium and nitrogen reaction in the CaCl2 material, eliminate residual calcium, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating CaCl2 as the carbon of preparation lithium ion battery negative material.
With above-mentioned negative material: polyacrylic acid ethanolic solution (5wt%) is 90: 10 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: acetylene black: the polyacrylic acid aqueous solution (5wt%) is 95: 5: 5 in mass ratio, and mechanical mixture 30 minutes is modulated into paste, is coated on the aluminium film, the final vacuum drying of drying in the shade; At 100 Kg cm
-2Pressure under compressing, obtain LiCoO
2Anodal.
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, consist of lithium ion battery.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
Embodiment three: carbon coats Ca
3N
2Lithium battery (2) for negative pole
Get purity and be 99.99% calcium metal, 850
oAfter the C fusing, with High Purity Nitrogen (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, the calcium droplet generates CaCl2 (Ca with the nitrogen reaction in blanket of nitrogen
3N
2) microballoon, be 800 at molecular weight, purity is to form spherical powder in 99% the polyethylene glycol liquid after the cooling; Meanwhile, the polyethylene glycol generation carbonization that contacts with CaCl2, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats CaCl2 material primary product.
Filter out carbon and coat Ca
3N
2Primary product is again calcined in the atmosphere of the High Purity Nitrogen of purity 99.999% and was made with extra care in 3 hours, and temperature is controlled at 650
oBelow the C, make carbon coat residual calcium and nitrogen reaction in the CaCl2 material, eliminate residual calcium, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating CaCl2 as the carbon of preparation lithium ion battery negative material.
With above-mentioned negative material: polyacrylic acid ethanolic solution (5wt%) is 90: 10 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 LiMnO
2: acetylene black: the polyacrylic acid aqueous solution (5wt%) is 95: 5: 5 in mass ratio, and mechanical mixture 30 minutes is modulated into paste, is coated on the aluminium film, the final vacuum drying of drying in the shade; At 100 Kg cm
-2Pressure under compressing, obtain LiMnO
2Anodal.
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, consist of lithium ion battery.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
Embodiment four: carbon coats Ca
3N
2-Ca
2The N mixture is the lithium battery of negative pole
Get purity and be 99.99% calcium metal, 850
oAfter the C fusing, with High Purity Nitrogen (purity 99.999%) spraying, be ejected in the polyethylene glycol liquid, the calcium droplet generates CaCl2 (Ca with the nitrogen reaction in blanket of nitrogen
3N
2) microballoon, be 400 at molecular weight, purity is to form spherical powder in 99% the polyethylene glycol liquid after the cooling; Meanwhile, the polyethylene glycol generation carbonization that contacts with CaCl2, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats CaCl2 material primary product.
Filter out carbon and coat Ca
3N
2Primary product is again calcined in a vacuum and was made with extra care in 2.5 hours, and temperature is controlled at 700
oBelow the C, make carbon coat residual calcium and CaCl2 reaction in the CaCl2 material, generate Ca
2N, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating Ca as the carbon of preparation lithium ion battery negative material
3N
2-Ca
2The N mixture.
Above-mentioned carbon is coated Ca
3N
2-Ca
2The N mixture: polyacrylic acid ethanolic solution (5wt%) is 90: 10 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 LiFePO
4: acetylene black: the polyacrylic acid aqueous solution (5wt%) is 95: 5: 5 in mass ratio, and mechanical mixture 30 minutes is modulated into paste, is coated on the aluminium film, the final vacuum drying of drying in the shade; At 100 Kg cm
-2Pressure under compressing, obtain 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, consist of lithium ion battery.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.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 lithium cell cathode material preparation method of CaCl2, the steps include:
(1) gets after purity is the fusing of 99.99% calcium metal, with the High Purity Nitrogen spraying of purity 99.999%, be ejected into molecular weight and be 200 ~ 800, purity is that the calcium droplet generates Ca with the nitrogen reaction in 99% the polyethylene glycol liquid in blanket of nitrogen
3N
2Microballoon forms spherical powder after the cooling in polyethylene glycol liquid; Meanwhile, with Ca
3N
2The polyethylene glycol generation carbonization of contact, the gas that carbonisation produces makes the carbon film bulging, forms carbon and coats CaCl2 material primary product;
(2) filter out carbon and coat CaCl2 material primary product after, implement follow-up any treatment step:
In the atmosphere of the High Purity Nitrogen of purity 99.999%, again calcine and made with extra care in 2 ~ 3 hours, temperature is controlled at below 700 ℃, make carbon coat residual calcium and nitrogen reaction in the CaCl2 material primary product, eliminate residual calcium, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material primary product; After the cooling, namely obtain coating Ca as the carbon of preparation lithium ion battery negative material
3N
2Perhaps,
Again calcined in a vacuum 2 ~ 3 hours, temperature is controlled at below 700 ℃, makes carbon coat residual calcium and CaCl2 reaction in the CaCl2 material, generates Ca
2N, simultaneously further carbonization is to remove the polyethylene glycol that remains on the carbon coating CaCl2 material; After the cooling, namely obtain coating Ca as the carbon of preparation lithium ion battery negative material
3N
2-Ca
2The N mixture.
2. prepare the method for cathode of lithium battery with the described lithium cell cathode material of claim 1, the steps include: carbon is coated Ca
3N
2Or carbon coats Ca
3N
2-Ca
2The polyacrylic acid ethanolic solution of N mixture and 5wt% is 90: 10 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, namely obtain cathode of lithium battery.
3. with the lithium battery of the described negative material preparation of claim 1, be take microporous polypropylene membrane as barrier film, electrode material side anodal and negative pole forms sandwich structure, built-in electrolyte with barrier film in opposite directions; It is characterized in that this lithium battery is with LiCo
(1-x)Mn
xO
2Or LiFePO
4Be positive electrode, wherein 0≤x≤1; 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
4. lithium battery according to claim 3 is characterized in that, the preparation process of the positive pole of this lithium battery is:
LiCo in mass ratio
(1-x)Mn
xO
2Or LiFePO
4: the polyacrylic acid ethanolic solution of acetylene black: 5wt% is 95: 5: 5, and mechanical mixture 30 minutes is modulated into paste, is coated on the aluminium film, the final vacuum drying of drying in the shade; At 100 Kg cm
-2Pressure under compressing, obtain LiCo
(1-x)Mn
xO
2Positive pole or LiFePO
4Anodal.
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| CN102386378B (en) * | 2011-09-13 | 2016-03-02 | 东莞新能源科技有限公司 | A kind of preparation method of lithium ion battery electrode sizing agent |
| CN106006579B (en) * | 2016-05-18 | 2018-11-27 | 北京理工大学 | A kind of Ca2The preparation method of N |
| CN106058149B (en) * | 2016-05-18 | 2019-06-04 | 北京理工大学 | Electrode slice and preparation method thereof and sodium-ion battery |
| JP7022917B2 (en) * | 2017-07-14 | 2022-02-21 | パナソニックＩｐマネジメント株式会社 | Negative electrode active material and battery |
| KR102180203B1 (en) * | 2019-01-17 | 2020-11-18 | 서울대학교산학협력단 | Anode material of Lithium ion battery and method of preparing the same |
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| CN1184706C (en) * | 2002-03-15 | 2005-01-12 | 中国科学院上海微系统与信息技术研究所 | Ball milling process of preparing lithium nitride for negative electrode material of lithium ion battery |
| CN1291910C (en) * | 2002-07-02 | 2006-12-27 | 佛朗科伊斯·拉科斯特 | Method for calcium nitride synthesis |
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