CN104795538A - Solid-phase synthesis oxygen bearing bismuth fluoride anode material for lithium ion battery and preparation method thereof - Google Patents
Solid-phase synthesis oxygen bearing bismuth fluoride anode material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN104795538A CN104795538A CN201510197142.6A CN201510197142A CN104795538A CN 104795538 A CN104795538 A CN 104795538A CN 201510197142 A CN201510197142 A CN 201510197142A CN 104795538 A CN104795538 A CN 104795538A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
Abstract
The invention relates to a solid-phase synthesis oxygen bearing bismuth fluoride anode material for a lithium ion battery and a preparation method of the solid-phase synthesis oxygen bearing bismuth fluoride anode material. The preparation method comprises the following steps: a quaternary ammonium salt taking fluoride as an anion is taken as a raw material, the raw material is in solid-phase synthesis into bismuth fluoride by steric hindrance of a macroradical and the action of a specific additive directly, and at the same time, oxygen permeates into a lattice in an ozone atmosphere, so that the electronic conductivity of material is improved greatly; high-purity bismuth fluoride is taken as a cathode material for a secondary battery, and has specific capacity exceeding 200 mAh.g<-1>. The preparation method is low in equipment requirement, the product is high in purity, reaction by-products such as various complex salts for producing bismuth fluoride in the solid-phase reaction can be avoided, and the solid-phase synthesis oxygen bearing bismuth fluoride anode material has excellent electrochemical performance.
Description
Technical field
The present invention relates to a kind of high power capacity and fluoridize bismuth complex lithium electricity positive electrode manufacture method technical field.
Background technology
Lithium rechargeable battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, have dollar of/year share more than 30,000,000,000 in global portable power source market at present and increase gradually with the speed more than 10%.Particularly in recent years, along with petering out of fossil energy, the new forms of energy such as solar energy, wind energy, biomass energy become the alternative of traditional energy gradually, and wherein wind energy, solar energy have intermittence, use a large amount of energy-storage batteries for meeting the supply of electric power needs continued simultaneously; The urban air-quality problem that vehicle exhaust brings is day by day serious, and instant stage has been arrived in vigorously advocating and developing of electric motor car (EV) or hybrid electric vehicle (HEV); These demands provide lithium ion battery explosive growth point, also have higher requirement to the performance of lithium ion battery simultaneously.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal that scientific and technical personnel study, and the research and development of high power capacity positive electrode can alleviate that current Li-ion batteries piles volume is large, heavy weight, price are high-leveled and difficult with the situation meeting high power consumption and high-power equipment needs.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time between 100-180mAh/g, positive electrode specific capacity is low has become the bottleneck promoting lithium ion battery specific energy.The positive electrode that the lithium ion battery of current commercialization is the most practical is LiCoO
2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years, the researcher of countries in the world is devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the lithium ion cell positive filtered out nearly tens of kinds, but really have potential commercial applications prospect or occurred that positive electrode is commercially very few really.As lithium manganate having spinel structure LiMn
2o
4, its cost is lower, and than being easier to preparation, security performance is also relatively good, but capacity is lower, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation hold facility is not good, and under high temperature, capacity attenuation is very fast, Mn
3+john-Teller effect and dissolving in the electrolyte annoying researcher for a long time.The LiNiO of layer structure
2and LiMnO
2although there is larger theoretical specific capacity, be respectively 275mAh/g and 285mAh/g, their preparations are very difficult, and poor heat stability, cyclicity is very poor, and capacity attenuation is very fast.And current progressively business-like LiFePO4 LiFePO
4cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity about only has 170mAh/g, and actual capacity is in about 140mAh/g [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1:123-128.].What have market prospects at present only has lithium vanadate Li more than the positive electrode of 200mAh/g specific capacity
1+xv
3o
8, Li
1+xv
3o
8material can have and has even close to the capacity of 300mAh/g, but its electric discharge average voltage is lower and also in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly the high lithium of manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system compares positive electrode, there is the cost more than the Capacity Ratio of 200mAh/g, higher thermal stability and relative moderate and receive the concern of people, but performance under this material high magnification is very undesirable, limit its application [Young-Sik Hong in electrokinetic cell, Yong Joon Park, et al., Solid State Ionics, 2005,176:1035-1042].
In recent years, fluoride positive electrode enters the visual field of researcher because its capacity is high, the prices of raw and semifnished materials are low.The operation principle of fluoride materials and conventional lithium ion battery positive electrode is different, all there is lithium ion and can embed or the space of deintercalation in traditional lithium ion cell positive and negative pole, and the lithium ion in electrolyte embeds between a positive electrode and a negative electrode back and forth and deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.Fluoride is then a kind of transition material, namely in whole discharge process, although Me has nothing in common with each other, and MeF
nsimilar change [Badway F, Cosandey F, Pereira N, etal., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10): A1318-A1327.] as follows can be there is:
nLi
++MeF
n+ne
-→nLiF+Me
0
Can discharge in this process far more than 200mAh.g
-1specific capacity, thus obtain investigation of materials personnel height attention.Wherein fluoridize bismuth owing to there being about 7170WhL
-1volume and capacity ratio and have huge advantage.The conventional synthetic method of fluoridizing bismuth is at high temperature reacting with hydrogen fluoride gas and metal oxide/hydroxide or fluorine gas and metal simple-substance, and process conditions harshness, equipment requirement is very high, and energy consumption is high, and therefore price is very expensive.Liquid phase reactor preparation fluoridizes bismuth then often because too high cannot the use as positive electrode of by-products content also lacks economy because the many costs of generation waste liquid are high simultaneously.Fluoridizing bismuth also has a negative characteristic to be namely that its electronic conductivity is extremely low as lithium ion secondary battery anode material, therefore can cause very high polarizing voltage in charge and discharge process.Ion doping is a kind of microstructure of effective adjustment lattice, changes the means of lattice electron and ionic transport properties, likely improves the chemical property of material.But it is very complicated to the mechanism of action of parent that ion doping or even polyion work in coordination with doping, effect is often difficult to expect.
Therefore develop that a kind of technique is simple, constant product quality, there is excellent electrochemical performance synthesis in solid state fluoridize bismuth preparation method and fluoridize the key that bismuth material applies as secondary cell.
Summary of the invention
The present invention is directed to existing background technology to propose a kind of synthesis in solid state containing oxygen and fluoridize bismuth anode material for lithium-ion batteries and preparation method thereof, the method employing is the quaternary ammonium salt of anion with fluorine is raw material, directly synthesized by the effect solid phase of specific adjuvant fluoridize bismuth by the space steric effect of macoradical, in lattice, infiltrate oxygen by ozone atmosphere simultaneously and increase substantially the electronic conductivity of material, this is fluoridized bismuth material and has more than 200mAh.g as anode material for lithium-ion batteries use
-1specific capacity.The method equipment requirement is low, and product purity is high, can avoid generating in solid phase reaction and fluoridizes the side reaction products such as the multiple double salt of bismuth and have excellent chemical property.
This synthesis in solid state fluoridizes bismuth preparation method containing oxygen, it is characterized by: after being mixed by the auxiliary agent Z1 of bismuth salt and bismuth salt quality 0.5-2%, put into ball mill, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10-20 hour of 200-400 rev/min, this material is called material I; By with fluorine be anion quaternary ammonium salt, with fluorine be the 0.5-2% of the quaternary ammonium salt quality of anion auxiliary agent Z2, with fluorine be the quaternary ammonium salt quality of anion 2-4% absolute ethyl alcohol mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10-20 hour of 200-400 rev/min, this material is called material II; Material I, material II are put into ball mill, ball milling is 20: 1 with the mass ratio of material, in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is simultaneously the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 5-10 hour of 300-400 rev/min; Material after taking-up ball milling, after three washings, obtains this at 100 DEG C-120 DEG C drying box inner dryings and fluoridizes bismuth containing oxygen after 10-20 hour.
Bismuth salt in preparation method as above is the one in five nitric hydrate bismuths, bismuth chloride; Auxiliary agent Z1 is the one in perfluoro-heptanoic acid, 2,2-difluoro cyclopropyl carboxylic acids, perfluoroglutaric acid; Auxiliary agent Z2 is the one in Tween-60, op-10, Arlacel-80; Take fluorine as the quaternary ammonium salt of anion be tetra-n-butyl ammonium fluoride, one in Methanaminium, N,N,N-trimethyl-, fluoride, benzyl trimethyl ammonium fluoride; In material I, the amount of substance of bismuth salt is 1: 3 with the ratio of the amount of quaternary ammonium material in material II.
Fig. 1 is charging capacity, discharge capacity and efficiency for charge-discharge figure, voltage range 1.8V-4.0V, the charging and discharging currents 0.1C of front 10 circulations of this material.
Compared with prior art, the invention has the advantages that: adopting with fluorine be the quaternary ammonium salt of anion is raw material, directly synthesized by the effect solid phase of specific adjuvant fluoridize bismuth by the space steric effect of macoradical, in lattice, infiltrate oxygen by ozone atmosphere simultaneously and increase substantially the electronic conductivity of material, this is fluoridized bismuth material and has more than 200mAh.g as anode material for lithium-ion batteries use
-1specific capacity.The method equipment requirement is low, and product purity is high, can avoid generating in solid phase reaction and fluoridizes the side reaction products such as the multiple double salt of bismuth and have excellent chemical property.
Accompanying drawing explanation
The charging capacity of front 10 circulations of this material of Fig. 1, discharge capacity and efficiency for charge-discharge figure, voltage range 1.8V-4.0V, charging and discharging currents 0.1C.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: put into ball mill by after the mixing of the perfluoro-heptanoic acid of five nitric hydrate bismuths and five nitric hydrate bismuth quality 0.5%, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10 hours of 200 revs/min, this material is called material I; Ball mill is put into after being mixed by the absolute ethyl alcohol of the Tween-60 of 0.5% of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium fluoride quality, 2% of tetra-n-butyl ammonium fluoride quality, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10 hours of 200 revs/min, this material is called material II; Material I and material II is put into ball mill according to the amount of substance of bismuth salt in material I with the ratio that the ratio of the amount of quaternary ammonium material in material II is 1: 3, ball milling is 20: 1 with the mass ratio of material, simultaneously in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 5 hours of 300 revs/min; Material after taking-up ball milling, after three washings, obtains this at 100 DEG C of drying box inner dryings and fluoridizes bismuth containing oxygen after 10 hours.
Embodiment 2: put into ball mill by after 2,2-difluoro cyclopropyl carboxylic acids mixing of bismuth chloride and bismuth chloride quality 1%, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 15 hours of 300 revs/min, is called material I by this material; Ball mill is put into after being mixed by the absolute ethyl alcohol of the op-10 of 1% of Methanaminium, N,N,N-trimethyl-, fluoride, Methanaminium, N,N,N-trimethyl-, fluoride quality, 3% of Methanaminium, N,N,N-trimethyl-, fluoride quality, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 15 hours of 300 revs/min, this material is called material II; Material I and material II is put into ball mill according to the amount of substance of bismuth salt in material I with the ratio that the ratio of the amount of quaternary ammonium material in material II is 1: 3, ball milling is 20: 1 with the mass ratio of material, simultaneously in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 7 hours of 350 revs/min; Material after taking-up ball milling, after three washings, obtains this at 110 DEG C of drying box inner dryings and fluoridizes bismuth containing oxygen after 15 hours.
Embodiment 3: put into ball mill by after the mixing of the perfluoroglutaric acid of bismuth chloride and bismuth chloride quality 2%, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 20 hours of 400 revs/min, this material is called material I; Ball mill is put into after being mixed by the absolute ethyl alcohol of the auxiliary agent Arlacel-80 of 2% of benzyl trimethyl ammonium fluoride, benzyl trimethyl ammonium fluoride quality, 4% of benzyl trimethyl ammonium fluoride quality, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 20 hours of 400 revs/min, this material is called material II; Material I and material II is put into ball mill according to the amount of substance of bismuth salt in material I with the ratio that the ratio of the amount of quaternary ammonium material in material II is 1: 3, ball milling is 20: 1 with the mass ratio of material, simultaneously in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 10 hours of 400 revs/min; Material after taking-up ball milling, after three washings, obtains this at 120 DEG C of drying box inner dryings and fluoridizes bismuth containing oxygen after 20 hours.
Embodiment 4: put into ball mill by after the mixing of the perfluoroglutaric acid of five nitric hydrate bismuths and five nitric hydrate bismuth quality 0.7%, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 13 hours of 350 revs/min, this material is called material I; Ball mill is put into after being mixed by the absolute ethyl alcohol of the Arlacel-80 of 1.5% of benzyl trimethyl ammonium fluoride, benzyl trimethyl ammonium fluoride quality, 3.5% of benzyl trimethyl ammonium fluoride quality, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 17 hours of 300 revs/min, this material is called material II; Material I and material II is put into ball mill according to the amount of substance of bismuth salt in material I with the ratio that the ratio of the amount of quaternary ammonium material in material II is 1: 3, ball milling is 20: 1 with the mass ratio of material, simultaneously in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 8 hours of 380 revs/min; Material after taking-up ball milling, after three washings, obtains this at 115 DEG C of drying box inner dryings and fluoridizes bismuth containing oxygen after 15 hours.
Embodiment 5: put into ball mill by after the mixing of the perfluoroglutaric acid of five nitric hydrate bismuths and five nitric hydrate bismuth quality 0.5%, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 20 hours of 200 revs/min, this material is called material I; Ball mill is put into after being mixed by the absolute ethyl alcohol of the Arlacel-80 of 1% of Methanaminium, N,N,N-trimethyl-, fluoride, Methanaminium, N,N,N-trimethyl-, fluoride quality, 3% of Methanaminium, N,N,N-trimethyl-, fluoride quality, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 15 hours of 200 revs/min, this material is called material II; Material I and material II is put into ball mill according to the amount of substance of bismuth salt in material I with the ratio that the ratio of the amount of quaternary ammonium material in material II is 1: 3, ball milling is 20: 1 with the mass ratio of material, simultaneously in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 7 hours of 350 revs/min; Material after taking-up ball milling, after three washings, obtains this at 120 DEG C of drying box inner dryings and fluoridizes bismuth containing oxygen after 19 hours.
Claims (2)
1. a synthesis in solid state fluoridizes bismuth anode material for lithium-ion batteries and preparation method thereof containing oxygen, ball mill is put into after it is characterized in that the auxiliary agent Z1 of bismuth salt and bismuth salt quality 0.5-2% to mix, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10-20 hour of 200-400 rev/min, this material is called material I; By with fluorine be anion quaternary ammonium salt, with fluorine be the 0.5-2% of the quaternary ammonium salt quality of anion auxiliary agent Z2, with fluorine be the quaternary ammonium salt quality of anion 2-4% absolute ethyl alcohol mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10-20 hour of 200-400 rev/min, this material is called material II; Material I, material II are put into ball mill, ball milling is 20: 1 with the mass ratio of material, in ball grinder, charged pressure is 5 atmospheric pressure volume ratios is simultaneously the argon gas of 80: 20 and the mist of ozone, with the speed ball milling 5-10 hour of 300-400 rev/min; Material after taking-up ball milling, after three washings, obtains this at 100 DEG C-120 DEG C drying box inner dryings and fluoridizes bismuth containing oxygen after 10-20 hour;
Bismuth salt in preparation method as above is the one in five nitric hydrate bismuths, bismuth chloride; Auxiliary agent Z1 is the one in perfluoro-heptanoic acid, 2,2-difluoro cyclopropyl carboxylic acids, perfluoroglutaric acid; Auxiliary agent Z2 is the one in Tween-60, op-10, Arlacel-80; Take fluorine as the quaternary ammonium salt of anion be tetra-n-butyl ammonium fluoride, one in Methanaminium, N,N,N-trimethyl-, fluoride, benzyl trimethyl ammonium fluoride; In material I, the amount of substance of bismuth salt is 1: 3 with the ratio of the amount of quaternary ammonium material in material II.
2. synthesis in solid state according to claim 1 fluoridizes bismuth anode material for lithium-ion batteries and preparation method thereof containing oxygen, it is characterized in that the bismuth of fluoridizing prepared has more than 200mAh.g
-1specific capacity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742603A (en) * | 2016-03-29 | 2016-07-06 | 宁波大学 | Lithium battery positive electrode material with Bi2O3/BiF<3-2x>O<x>/Zn<2+> and Mg<2+> doping bismuth fluoride layer structure and preparation method of lithium battery cathode material |
| CN105742632A (en) * | 2016-03-29 | 2016-07-06 | 宁波大学 | Gradient structure coated Fe<3+> and B<3+> doping copper fluoride lithium battery positive electrode material and preparation method thereof |
| CN105845905A (en) * | 2016-03-29 | 2016-08-10 | 宁波大学 | Bismuth fluoride and copper fluoride composite lithium ion battery positive electrode material with gradient coating layer, and preparation method therefor |
| CN105914350A (en) * | 2016-03-29 | 2016-08-31 | 宁波大学 | Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of lithium battery and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070190414A1 (en) * | 2004-10-01 | 2007-08-16 | Rutgers, The State University | Bismuth oxyfluoride based nanocomposites as electrode materials |
| US20070243466A1 (en) * | 2004-10-01 | 2007-10-18 | Rutgers, The State University | Bismuth Fluoride Based Nanocomposites as Electrode Materials |
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN102299328A (en) * | 2011-08-31 | 2011-12-28 | 北京理工大学 | Metal fluoride cathode material of lithium secondary battery and preparation method of cathode material |
-
2015
- 2015-04-19 CN CN201510197142.6A patent/CN104795538B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070190414A1 (en) * | 2004-10-01 | 2007-08-16 | Rutgers, The State University | Bismuth oxyfluoride based nanocomposites as electrode materials |
| US20070243466A1 (en) * | 2004-10-01 | 2007-10-18 | Rutgers, The State University | Bismuth Fluoride Based Nanocomposites as Electrode Materials |
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN102299328A (en) * | 2011-08-31 | 2011-12-28 | 北京理工大学 | Metal fluoride cathode material of lithium secondary battery and preparation method of cathode material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742603A (en) * | 2016-03-29 | 2016-07-06 | 宁波大学 | Lithium battery positive electrode material with Bi2O3/BiF<3-2x>O<x>/Zn<2+> and Mg<2+> doping bismuth fluoride layer structure and preparation method of lithium battery cathode material |
| CN105742632A (en) * | 2016-03-29 | 2016-07-06 | 宁波大学 | Gradient structure coated Fe<3+> and B<3+> doping copper fluoride lithium battery positive electrode material and preparation method thereof |
| CN105845905A (en) * | 2016-03-29 | 2016-08-10 | 宁波大学 | Bismuth fluoride and copper fluoride composite lithium ion battery positive electrode material with gradient coating layer, and preparation method therefor |
| CN105914350A (en) * | 2016-03-29 | 2016-08-31 | 宁波大学 | Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of lithium battery and preparation method thereof |
| CN105845905B (en) * | 2016-03-29 | 2020-04-03 | 宁波大学 | Bismuth fluoride and copper fluoride composite lithium battery positive electrode material with gradient coating layer and preparation method thereof |
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