CN102386403B - Preparation method for magnesium/barium-activated lithium iron phosphate cathode material - Google Patents
Preparation method for magnesium/barium-activated lithium iron phosphate cathode material Download PDFInfo
- Publication number
- CN102386403B CN102386403B CN201110337701.0A CN201110337701A CN102386403B CN 102386403 B CN102386403 B CN 102386403B CN 201110337701 A CN201110337701 A CN 201110337701A CN 102386403 B CN102386403 B CN 102386403B
- Authority
- CN
- China
- Prior art keywords
- barium
- magnesium
- lithium
- iron phosphate
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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 discloses a preparation method for a magnesium/barium-activated lithium iron phosphate cathode material. The preparation method is characterized by comprising the following steps of: mixing raw materials which are a lithium source, an iron source, a phosphate group source, a magnesium source and a barium source in the molar ratio of 1:(0.002-0.005):(0.0003-0.003):1:1, ball-milling the mixture for 20h at the high rotating speed of 200r/mimn in an absolute ethanol medium, drying the mixture at 105 to 120 DEG C to obtain a precursor, arranging the dried precursor in a high-temperature furnace, and sintering the precursor for 24h at the high temperature of 500 to 750 DEG C to obtain the magnesium/barium-activated lithium iron phosphate cathode material. Due to the doping of a small amount of substitutional magnesium/barium, so control over the appearance and grain size of the product is facilitated, a stable lithium iron phosphate compound is obtained, the crystal lattice of the compound is activated, a lithium ion diffusion coefficient is increased and the first discharging capacity of a battery adopting the obtained material reaches 155.52mAh/g. The potential of a charging and discharging platform relative to a lithium electrode is about 3.5V, the initial discharging capacity of the battery exceeds 164mAh/g, and the capacity of the battery is attenuated by about 3.0 percent after 100 charging and discharging cycles. Compared with those of the control embodiment of undoped LiFePO4, the material prepared by the method has the advantages that: specific capacity and cyclical stability are relatively more improved. The cost of barium is a hundred times lower than that of lithium, so production cost can be decreased by over ten times.
Description
Technical field
Magnesium of the present invention, barium activation lithium iron phosphate positive material preparation method, belong to a kind of anode material of lithium battery preparation method, particularly a kind of lithium iron phosphate battery positive material preparation method.
Background technology
At present, the Present study of LiFePO4 doping vario-property: LiFePO4 LiFePO4 is because it is nontoxic, environmentally friendly, safe, raw material source is abundant, specific capacity is high, stable cycle performance, cheap, there is the steady discharge platform of the theoretical capacity 3.5V of 170mAh/g, LiFePO 4 material has high energy density, cheap price, excellent fail safe, is specially adapted to electrokinetic cell.But its resistivity is larger.Due to LiFePO4, under normal temperature, the dynamics of LiFePO4 is bad, high rate performance extreme difference, researchers both domestic and external have used and have improved high rate performance methods such as coated, doping, nanometer, and basic idea improves exactly conductivity and shortens ion, electric transmission path.Doping is the important material modification method of a class.2002, the reported first lithium position doping vario-properties such as Massachusetts science and engineering Chiang professor Yet-Ming can improve LiFePO4 electronic conductivity greatly.They carry out the doping of high volence metal ion (Mg2+, Al3+, Ti4+, Zr4+, Nb5+ and W6+) solid solution in lithium position, electronic conductivity has improved 8 orders of magnitude.Sample through above-mentioned doping has good chemical property, particularly high-rate performance, under the electric current of 21.5C (3225mA/g), discharges, and still can obtain the capacity of 60mAh/g.Doping carbon: carbon has good electric conductivity and lower mass density, adds a small amount of carbon of people, can improve on the one hand the electric conductivity of material, can reduce on the other hand the particle diameter yardstick of material.Xxx has studied different phase and has mixed the impact of people's carbon on material electrochemical performance.Shi Zhicong etc. " adopt solid phase reaction in conjunction with high speed ball-milling method, synthetic positive electrode LiFePO4, experiment shows: LiFePO4 has the discharge voltage plateau of 3.4V, discharge capacity reaches 147mAh/g charge and discharge cycles and only decays 9.5% afterwards 100 times first.LiFePO4/C composite material after carbon dope, granule-morphology rule, spherical for class, particle is little, and particle diameter distributes and all hooks.Carbon is scattered between crystal grain, has strengthened the electrical conductance between particle.LiFePO4 specific discharge capacity and cycle performance after carbon dope all significantly improve.Lithium position doping: LiFePO4 crushed grain is assorted is a kind of important method of improving chemical property.The doping of lithium position can improve the conductivity of LiFePO4.Tan Xianyan etc. " " adopt calcination method synthesizing lithium ionic cell positive pole material lithium iron phosphate, mix a small amount of Mg2+ and significantly improved the conductivity of material, have improved the chemical property of LiFePO4.After doping, LiFePO4 first discharge capacity reaches 135.52mAh/g; Unadulterated LiFePO4 first discharge capacity only has 116.25mAh/g.Conductivity after doping has obtained certain raising.This is because a small amount of metal ion of doping replaces Li+ position, forms p-type semiconductor, has increased the conductivity of material.The identical ^ of Liu adopts improved solid phase method to prepare LiFePO4 and the Li0 that particle is fine, particle diameter is evenly distributed, 98Mn, and o.o2LiFePO4 compound, doping is conducive to control pattern and the particle diameter of product on a small quantity, obtains stable LiFePO4 compound.Because Mn2+ octahedral coordination radius is less than Fe2+, can think that magnesium ion occupies replacement lithium ion.Result shows: in material, the relative lithium electrode current potential of the charge and discharge platform of lithium ion is 3.5V left and right, and initial discharge capacity exceedes 160mAh/g, and after 50 charge and discharge cycles, capacity only decays 5.5%, shows that the method has improved specific energy and cyclical stability.Iron position is disastrously assorted: although the doping of lithium position can improve the conductivity of material, because foreign atom can hinder the diffusion of lithium ion in one dimension passage, thereby be unfavorable for improving the high-rate charge-discharge capability of material.And the doping of iron position can improve the rate charge-discharge performance of LiFePO4, improve cycle performance.The ^ such as Liu Fangling adopt parcel carbon to improve its surface electronic conductivity, and doped metal ion is to improve its body electronic conductivity.Having chosen ionic radius approaches and 4 different metal ion species Ca3+ of valence state, Ti5+, Ta5+, the Fe position doping of MO6+, sample unit cell volume after doping all has minimizing, electronic conductivity has improved 4-6 the order of magnitude than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is greatly reduced, and chemical property also obviously improves.The ^ such as Hu Huanyu adopt the synthetic tiny uniform nanoscale positive electrode LiFePO4 of particle of high-temperature solid phase reaction method, have good capacity circulating performance, but its high rate capability are poor.Mix a small amount of manganese and can reduce the polarization of material, improve the high rate capability of material.This is mainly the unit cell volume that has increased LiFePO4 due to the doping of manganese, more be conducive to deviating from of lithium, the doping of manganese has caused sintering process to produce crystal structure defects in addition, has improved the electron conduction of material, thereby the high-rate charge-discharge capability of material is made moderate progress.Phosphate potential crushed grain is assorted: P site doped is feasible in theory, but seldom has the doping of carrying out separately phosphate potential.The ^ such as Zhang Yurong have studied olivine structural Li2+2xTi2-xCu2x (NbO) 2, and by Ti and Cu replacement P, having obtained conductivity is that 1.26 × 10-6S/cm-adds, the positive electrode that initial discharge capacity is 805.8mAh/g.Such material has higher conductivity, but because Fe is all replaced by Ti and Cu, ' guiding discharge voltage is lower, and cycle performance is poor.Although phosphate potential is feasible in theory, study relatively less.
Through retrieval, record at present 1043 of relevant lithium battery applications for a patent for invention, 2181 of lithium ion battery applications for a patent for invention, wherein having a great deal of is relevant method of adulterating.
Be confirmed to be in theory lithium position, or iron position, or phosphate potential is adulterated and role, and relevant authoritative experts, still have different separately brilliant idea, also constantly studying, exploring.
Current more consistent viewpoint is, the advantage such as LiFePO4 has that fail safe is good, pollution-free, stable cycle performance, specific capacity are high and cheap, but also there is poorly conductive and the lower shortcoming of tap density.Poorly conductive is the biggest factor that affects LiFePO4 application, by doping, conductivity can be improved, and high-rate charge-discharge capability also improves, and has suppressed to a certain extent the effect of capacity attenuation.Doping approach can improve, improve lithium ion anode material performance, has been a kind of feasible mode of generally acknowledging.
summary of the invention
The object of the invention is to: the structural limitations of the lithium iron phosphate positive material (LiFePO4) based on prior art, there is its poorly conductive and the low deficiency of lithium ion diffusion coefficient, now propose magnesium, barium activation lithium iron phosphate positive material preparation method that the activation of a kind of magnesium, barium improves its performance.
The present invention, in view of doping approach can improve, improve lithium ion anode material performance, has been a kind of feasible mode of generally acknowledging.According to the chemical property of barium/lithium, electric property, crystal structure characteristic is the feature of akin element:
Barium, is element the most active in alkaline-earth metal, because it is very active, and easily oxidized, should be kept in kerosene and atoleine.
5.212 electron-volts of ionization energy, the first ionization energy 502.9kJ/mol;
Crystal structure: structure cell is body centred cubic cell, each structure cell contains 2 metallic atoms;
Cell parameter: a=502.8pm; B=502.8pm; C=502.8pm; α=90 °; β=90 °; γ=90 °.
Lithium, metallic element, can react with a large amount of inorganic reagents and organic reagent.With all energy chemical combination such as oxygen, nitrogen, sulphur, due to easily oxidated and dimmed, and density ratio kerosene is little, therefore should deposit in atoleine.
5.392 electron-volts of ionization energy, the first ionization energy 520.2kJ/mol;
Crystal structure: structure cell is body centred cubic cell, each structure cell contains 2 metallic atoms;
Cell parameter: a=351pm; B=351pm; C=351pm; α=90 °; β=90 °; γ=90 °.
Think that barium should be to be easy to lithium position chanza most.The present invention be by barium, adulterate test, in the situation with barium doping, can add again 1-2 other element, form 2 yuan or 3 yuan of doping, to obtain the good anode material of lithium battery of performance.
Magnesium of the present invention, barium activation lithium iron phosphate positive material, is characterized in that: its chemical composition or chemical general formula can be expressed as: LiMgx Bay Fe PO4, x==0.002-0.005, y=0.0003; Wherein the mol of Li, Mg, Ba, Fe, P ratio is: 1mol Li: 0.002-0.005mol Mg: 0.0003mol Ba: 1mol Fe: 1mol P.
Magnesium of the present invention, barium activation lithium iron phosphate positive material preparation method, it is characterized in that: its lithium source, source of iron, phosphoric acid root, magnesium source, the raw material in barium source, according to 1mol Li: 0.002-0.005molMg: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained is placed in high temperature furnace, in nitrogen atmosphere, through 500-750 ℃ of high-temperature calcination 16-24h, obtain magnesium of the present invention, barium activation lithium iron phosphate positive material.Its chemical composition is: LiMgx Bay Fe PO4, x==0.002-0.005, y=0.0003; Wherein the mol of Li, Mg, Ba, Fe, P ratio is: 1mol Li: 0.002-0.005mol Mg: 0.0003mol Ba: 1mol Fe: 1mol P.Its lithium source is one of lithium carbonate, lithium hydroxide, source of iron is ferrous oxalate, phosphoric acid root is one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate, and magnesium source is one of magnesium carbonate, magnesium oxide, magnesium hydroxide, and barium source is one of brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
The present invention's beneficial effect compared with prior art: magnesium of the present invention, barium activation lithium iron phosphate positive material preparation method, resulting materials replaces magnesium, barium because doping is a small amount of, be conducive to control pattern and the particle diameter of product, obtain stable LiFePO4 compound, barium ions occupies replacement lithium ion, its lattice has obtained activation, has improved lithium ion diffusion coefficient; The Fe position doping of Mg, the product unit cell volume after doping all has minimizing, and electronic conductivity improves than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is greatly reduced, and chemical property also obviously improves; Its first discharge capacity reach 155.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity exceedes 164mAh/g, capacity 3.0% left and right of approximately decaying after 100 charge and discharge cycles; Specific capacity and cyclical stability and unadulterated LiFePO4 first discharge capacity only have compared with 116.25mAh/g, are greatly improved.Because the price of magnesium, barium is than lithium price more than low hundred times, production cost can fall more than ten times.
Below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited to this.
Below adopt calcination method synthetic method, to magnesium of the present invention, barium activation lithium iron phosphate positive material, be illustrated.
Magnesium of the present invention, barium activation lithium iron phosphate positive material preparation method, its lithium source can be used: the lithium salts such as lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, source of iron can be used: ferrous oxalate etc., phosphoric acid root can be used: ammonium dihydrogen phosphate or diammonium hydrogen phosphate etc., magnesium source is, magnesium oxide (MgO), magnesium carbonate (MgCO3), magnesium hydroxide (Mg (OH) 2), barium source can be used: the barium salts such as brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
Select: lithium carbonate (Li2CO3) (99.73%), magnesium carbonate (99.5%), brium carbonate (BaCO3) (99.8%), ferrous oxalate (FeC2O4.2H2O) (99.06%), diammonium hydrogen phosphate (NH4H2PO4) (98%) is raw material; According to 1mol Li: 0.002-0.005mol Mg: 0.0003mol Ba: l mol Fe: after 1mol P ratio is mixed, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained is placed in high temperature furnace, in blanket of nitrogen, through 500-750 ℃ of high-temperature calcination 16-24h, obtain magnesium of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 1
Magnesium of the present invention, barium activation lithium iron phosphate positive material preparation method, by Li2CO3 (99.73%), magnesium carbonate (99.5%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, according to 1mol Li: 0.002mol Mg: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/min.After 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained is placed in high temperature furnace, in common purity nitrogen (> 99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Obtain magnesium of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 2 (not mixing contrast)
By Li2CO3 (99.73%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, according to 1mol Li: 1mol Fe: after 1mol P ratio is mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/min.After 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained is placed in high temperature furnace, in common purity nitrogen (> 99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Obtain lithium ion anode material.
Adopt the testing equipment of prior art and the method for testing of prior art, magnesium, barium to above embodiment 1 activate lithium iron phosphate positive material, carry out test result be with the comparative examples 2 of not mixing:
The magnesium of the embodiment of the present invention 1, barium activation lithium iron phosphate positive material, more than discharge capacity reaches 155.52mAh/g first; Unadulterated LiFePO4 first discharge capacity only has in 116.25mAh/g.
The barium activation lithium iron phosphate positive material of the embodiment of the present invention 1, the relative lithium electrode current potential of its charge and discharge platform is 3.5V left and right, initial discharge capacity exceedes 164mAh/g, capacity 3.0% left and right of approximately decaying after 100 charge and discharge cycles.
Barium activation lithium iron phosphate positive material preparation method of the present invention, assorted after doping, the raising of resulting materials specific capacity and cyclical stability, this is perhaps because doping is a small amount of, to replace magnesium, barium, be conducive to control pattern and the particle diameter of product, obtain stable LiFePO4 compound, barium ions occupies replacement lithium ion, its lattice has obtained activation, has improved lithium ion diffusion coefficient; Although the doping of barium lithium position can improve the conductivity of material, due to doping ion, can hinder the diffusion of lithium ion in one dimension passage, thereby be unfavorable for improving the high-rate charge-discharge capability of material.And the doping of iron position can improve the rate charge-discharge performance of LiFePO4, improve cycle performance.Having chosen ionic radius Fe the position approaching and magnesium that valence state is different adulterates, product unit cell volume after doping all has minimizing, electronic conductivity improves than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is greatly reduced, and chemical property also obviously improves; Its first discharge capacity reach, 155.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity exceedes 164mAh/g, capacity 3.0% left and right of approximately decaying after 100 drink charge and discharge cycles; Specific capacity and cyclical stability and unadulterated LiFePO4 first discharge capacity only have compared with 116.25mAh/g, are greatly improved.Be to replace magnesium, barium because doping is a small amount of, be conducive to control pattern and the particle diameter of product, obtain stable LiFePO4 compound, its lattice has obtained activation, has improved the result of lithium ion diffusion coefficient.
Claims (1)
1. magnesium, a barium activation lithium iron phosphate positive material preparation method, is characterized in that: select: lithium carbonate, and magnesium carbonate, brium carbonate, ferrous oxalate, diammonium hydrogen phosphate is raw material; After mixing according to 1mol Li:0.002-0.005molMg:0.0003mol Ba:1mol Fe:1mol P ratio, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained is placed in high temperature furnace, in nitrogen atmosphere, through 500-750 ℃ of high-temperature calcination 16-24h, obtain magnesium, barium activation lithium iron phosphate positive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110337701.0A CN102386403B (en) | 2011-10-26 | 2011-10-26 | Preparation method for magnesium/barium-activated lithium iron phosphate cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110337701.0A CN102386403B (en) | 2011-10-26 | 2011-10-26 | Preparation method for magnesium/barium-activated lithium iron phosphate cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102386403A CN102386403A (en) | 2012-03-21 |
| CN102386403B true CN102386403B (en) | 2014-04-16 |
Family
ID=45825566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110337701.0A Active CN102386403B (en) | 2011-10-26 | 2011-10-26 | Preparation method for magnesium/barium-activated lithium iron phosphate cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102386403B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502537B (en) * | 2021-07-12 | 2022-04-12 | 重庆文理学院 | Method for synthesizing ternary barium-containing dicarbonate crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4703985B2 (en) * | 2004-08-02 | 2011-06-15 | 住友大阪セメント株式会社 | Method for producing positive electrode active material for lithium battery |
-
2011
- 2011-10-26 CN CN201110337701.0A patent/CN102386403B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-48991A 2006.02.16 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102386403A (en) | 2012-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102347486B (en) | Method for preparing barium-activated lithium iron phosphate cathode material | |
| CN102376954A (en) | Lithium iron phosphate anode material with activating aluminum and barium | |
| CN102376952B (en) | Preparing method for aluminium and barium activated lithium iron phosphate positive electrode material | |
| CN102509796B (en) | Preparation method of boron and barium activated lithium iron phosphate anode material | |
| CN102364734B (en) | Method for preparing antimony and barium activated lithium iron phosphate cathode material | |
| CN102386403B (en) | Preparation method for magnesium/barium-activated lithium iron phosphate cathode material | |
| CN102509798B (en) | Preparation method of copper-barium-activated lithium iron phosphate anode material | |
| CN102386406B (en) | Preparation method of selenium and barium activated lithium iron phosphate anode materials | |
| CN102376953B (en) | Preparing method for calcium and barium activated lithium iron phosphate positive electrode material | |
| CN102509793B (en) | Method for preparing zinc and barium activated lithium iron phosphate cathode material | |
| CN102509794B (en) | Preparation method of zirconium, barium activated lithium iron phosphate anode material | |
| CN102386396B (en) | Preparation method of niobium and barium activated lithium iron phosphate anode materials | |
| CN102354755B (en) | Preparation method of strontium and barium activated lithium iron phosphate positive pole material | |
| CN102437333B (en) | Preparation method of bismuth and barium activated lithium iron phosphate as cathode material | |
| CN102361078B (en) | Method for preparing nickel and barium activated lithium iron phosphate cathode material | |
| CN102364733B (en) | Method for preparing antimony and barium activated lithium iron phosphate cathode material | |
| CN102364735B (en) | Preparation method of beryllium and barium activated lithium iron phosphate positive electrode material | |
| CN102347491B (en) | Method for preparing cadmium-barium-activated lithium iron phosphate cathode material | |
| CN102386402B (en) | Preparation method of cobalt/barium activated lithium iron phosphate anode material | |
| CN102361083B (en) | Method for preparing vanadium and barium activated lithium iron phosphate anode material | |
| CN102386401B (en) | Method for preparing molybdenum barium activated lithium iron phosphate anode material | |
| CN102437332B (en) | Preparation method of manganese and barium activated lithium iron phosphate as cathode material | |
| CN102437328B (en) | Preparation method of germanium and barium activated lithium iron phosphate as cathode material | |
| CN102386404A (en) | Magnesium and barium activated lithium iron phosphate cathode material | |
| CN102386399A (en) | Cobalt and barium activated lithium iron phosphate anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 542800 the Guangxi Zhuang Autonomous Region Hezhou city beauty instrument Ceramics Co. Ltd Applicant after: Li Xianlan Address before: 542800 the Guangxi Zhuang Autonomous Region Hezhou City eight step District No. 40 West Lane Applicant before: Li Xianlan |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191031 Address after: No.678-15, Xinmin North Road, Wutong street, Tongxiang City, Jiaxing City, Zhejiang Province Patentee after: Tongxiang Levi new materials Co., Ltd. Address before: 542800 Guangxi Hezhou beauty porcelain Co., Ltd. Patentee before: Li Xianlan |
|
| TR01 | Transfer of patent right |