CN104795539A - Cathode material for laminar bismuth fluoride lithium ion battery of liquid phase synthesis Cu2+, fe3+doped sheet and its prepn - Google Patents
Cathode material for laminar bismuth fluoride lithium ion battery of liquid phase synthesis Cu2+, fe3+doped sheet and its prepn Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 239000007791 liquid phase Substances 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- BMLZESWWTTUETN-UHFFFAOYSA-K [Li][Bi](F)(F)F Chemical compound [Li][Bi](F)(F)F BMLZESWWTTUETN-UHFFFAOYSA-K 0.000 title abstract 3
- 239000010406 cathode material Substances 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910052797 bismuth Inorganic materials 0.000 claims description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 9
- 229920006362 Teflon® Polymers 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 claims description 4
- MJJJJEUEZVGFLW-UHFFFAOYSA-N 2-dodecyl-2-sulfobutanedioic acid Chemical group CCCCCCCCCCCCC(S(O)(=O)=O)(C(O)=O)CC(O)=O MJJJJEUEZVGFLW-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- HHLJUSLZGFYWKW-UHFFFAOYSA-N triethanolamine hydrochloride Chemical compound Cl.OCCN(CCO)CCO HHLJUSLZGFYWKW-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims description 3
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 claims description 3
- KMLMOVWSQPHQME-UHFFFAOYSA-N 2,2-difluorocyclopropane-1-carboxylic acid Chemical class OC(=O)C1CC1(F)F KMLMOVWSQPHQME-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000004087 circulation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- H01M4/582—Halogenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a Cu<2+> and Fe<3+> doped laminar bismuth fluoride lithium ion cell anode material prepared through liquid phase synthesis and a preparation method of the bismuth fluoride lithium ion cell anode material. According to the method, the laminar bismuth fluoride is prepared by taking a liquid phase reaction, designing the technological conditions and introducing a plurality of auxiliaries; the discharge platform voltage and the capacity retention performance of the material are improved by doping Cu<2+> and Fe<3+>; when the bismuth fluoride material is used as the lithium ion cell anode material, the specific capacity of the bismuth fluoride material is higher than 200 mAh/g<-1>. The method is low in equipment requirement, high in product purity, capable of avoiding generation of multiple side reaction products such as double salt of bismuth fluoride in the liquid phase reaction, and excellent in 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.
Crystal formation and the pattern of fluoridizing bismuth are in addition very large on electrons transport property impact in lattice, are therefore directly connected to the chemical property of lithium ion battery as charge/discharge rates, capacity and circulation volume hold facility; Ion doping is a kind of microstructure of effective adjustment lattice, changes the means of lattice electron and ionic transport properties, but it is very complicated to the mechanism of action of parent that ion doping or even polyion work in coordination with doping, and effect is often difficult to expect.
Therefore develop that a kind of technique is simple, constant product quality, the liquid phase synthesis with excellent electrochemical performance 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 and propose a kind of liquid phase synthesis Cu
2+, Fe
3+doping sheet fluoridizes bismuth anode material for lithium-ion batteries and preparation method thereof, and the method by liquid phase reactor, and by the design of process conditions and introduce multiple auxiliary agent and prepare sheet and fluoridize bismuth, and passes through Cu
2+, Fe
3+doping improves discharge platform voltage and the capacity hold facility of material, and 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 liquid phase reactor and fluoridizes the side reaction products such as the multiple double salt of bismuth and have excellent chemical property.
This liquid phase synthesis Cu
2+, Fe
3+doping sheet fluoridizes bismuth method for preparing anode material of lithium-ion battery, it is characterized by: preparation consists of the water solution A 200-300mL of 5-15wt% bismuth nitrate, 0.1-0.3wt% copper nitrate, 0.1-0.5wt% ferric nitrate, 1-5wt% dust technology, 0.1-0.5wt% auxiliary agent Z1, preparation consists of the ammonium fluoride of 15-45wt%, the aqueous solution B 200-300mL of 0.1-0.5wt% auxiliary agent Z2, water solution A is identical with the volume of aqueous solution B, and in aqueous solution B, the concentration of ammonium fluoride is 3 times of bismuth nitrate concentration in water solution A; Auxiliary agent Z3,0.1-0.5wt% of preparation 0.1-0.5wt% have the aqueous solution C of the auxiliary agent Z4 of cerium sulphate crystal effect; Aqueous solution C being put into volume is 2L, internal diameter is the 1/3-1/2 place to reactor cumulative volume in the cylindrical reactor of 15-20 centimetre, the temperature of aqueous solution C is arranged on 40-60 DEG C and uses Teflon stir oar to stir with the speed of 1200rpm-1500rpm simultaneously.Use peristaltic pump water solution A and aqueous solution B to be pumped into ad-hoc location in reactor with same speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete.The temperature of reactor is adjusted to 30-40 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 20-40 hour.Thereafter, through filtering, in the drying box of 100-150 DEG C, Cu is obtained after dry 10-20 hour
2+, Fe
3+doping sheet fluoridizes bismuth.
In preparation method as above, auxiliary agent Z1 is the one in monoethanolamine, triethanolamine, Triethanolammonium chloride; Auxiliary agent Z2 be mean molecule quantity at 10000-20000 polyvinyl alcohol, op-10, Tween-40; Auxiliary agent Z3 is the one in perfluoro-heptanoic acid, 2,2-difluoro cyclopropyl carboxylic acids, perfluoroglutaric acid; The auxiliary agent Z4 with cerium sulphate crystal effect is lauryl sulfosuccinic acid monoester disodium, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium, the one in Monododecylphosphate potassium;
In preparation method as above, the diameter of Teflon stir oar is less than the diameter of reactor 5 centimetres; The speed of peristaltic pump conveying water solution A and aqueous solution B is 0.1-1mL/ minute; Ad-hoc location as above refers to that water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.
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.Fig. 2 is the scanning electron microscope (SEM) photograph of this material, the pattern of visible sheet in figure.
Compared with prior art, the invention has the advantages that: the method by liquid phase reactor, and by the design of process conditions and introduce multiple auxiliary agent and prepare sheet and fluoridize bismuth, and passes through Cu
2+, Fe
3+doping improves discharge platform voltage and the capacity hold facility of material, and 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 liquid phase reactor 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.
The scanning electron microscope (SEM) photograph of this material of Fig. 2.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: preparation 200mL consists of the water solution A of 5wt% bismuth nitrate, 1wt% dust technology, 0.1wt% copper nitrate, 0.1wt% ferric nitrate, 0.1wt% monoethanolamine; Preparation 200mL consists of the ammonium fluoride of 15wt%, 0.1wt% mean molecule quantity at the aqueous solution B of 10000-20000 polyvinyl alcohol; Preparation consists of the aqueous solution C of 0.1wt% perfluoro-heptanoic acid, 0.1wt% lauryl sulfosuccinic acid monoester disodium; Aqueous solution C is put into 2L volume, and internal diameter is 1/3 place to reactor cumulative volume in the cylindrical reactor of 15 centimetres, the temperature of aqueous solution C is arranged on 40 DEG C and uses diameter to be that the Teflon stir oar of 10 centimetres stirs with the speed of 1250rpm simultaneously.Use peristaltic pump water solution A and aqueous solution B to be pumped into reactor with 0.1mL/ minute speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete.Water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 30 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 20 hours.Thereafter, through filtering, in the drying box of 100 DEG C, Cu is obtained after dry 10 hours
2+, Fe
3+doping sheet fluoridizes bismuth.
Embodiment 2: preparation 300mL consists of the water solution A of 15wt% bismuth nitrate, 0.3wt% copper nitrate, 0.4wt% ferric nitrate, 5wt% dust technology, 0.5wt% Triethanolammonium chloride; Preparation 300mL consists of the ammonium fluoride of 45wt%, 0.5wt% mean molecule quantity at the aqueous solution B of 10000-20000 polyvinyl alcohol; Preparation consists of 0.5wt%2, the aqueous solution C of 2-difluoro cyclopropyl carboxylic acid and 0.5wt% Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium; Aqueous solution C is put into 2L volume, and internal diameter is 1/2 place to reactor cumulative volume in the cylindrical reactor of 20 centimetres, the temperature of aqueous solution C is arranged on 60 DEG C and uses diameter to be that the Teflon stir oar of 15 centimetres stirs with the speed of 1500rpm simultaneously.Use peristaltic pump water solution A and aqueous solution B to be pumped into reactor with 1mL/ minute speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete.Water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 40 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 40 hours.Thereafter, through filtering, in the drying box of 150 DEG C, Cu is obtained after dry 20 hours
2+, Fe
3+doping sheet fluoridizes bismuth.
Embodiment 3: preparation 250mL consists of the water solution A containing 10wt% bismuth nitrate, 0.2wt% copper nitrate, 0.3wt% ferric nitrate, 3wt% dust technology, 0.3wt% triethanolamine; Preparation 250mL consists of the ammonium fluoride of 30wt%, the aqueous solution B of 0.3wt%op-10; Preparation consists of the aqueous solution C of 0.3wt% perfluoroglutaric acid and 0.3wt% Monododecylphosphate potassium; Aqueous solution C is put into 2L volume, and internal diameter is 2/5 place to reactor cumulative volume in the cylindrical reactor of 17 centimetres, the temperature of aqueous solution C is arranged on 50 DEG C and uses diameter to be that the Teflon stir oar of 12 centimetres stirs with the speed of 1350rpm simultaneously.Use peristaltic pump water solution A and aqueous solution B to be pumped into reactor with 0.5mL/ minute speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete.Water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 30 hours.Thereafter, through filtering, in the drying box of 120 DEG C, Cu is obtained after dry 15 hours
2+, Fe
3+doping sheet fluoridizes bismuth.
Embodiment 4: preparation 260mL consists of the water solution A of 7wt% bismuth nitrate, 0.1wt% copper nitrate, 0.5wt% ferric nitrate, 3wt% dust technology, 0.3wt% Triethanolammonium chloride; Preparation 260mL consists of the ammonium fluoride of 21wt%, the aqueous solution B of 0.4wt% Tween-40; Preparation consists of 0.4wt%2, the aqueous solution C of 2-difluoro cyclopropyl carboxylic acid and 0.4wt% Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium; Aqueous solution C is put into 2L volume, and internal diameter is 2/5 place to reactor cumulative volume in the cylindrical reactor of 18 centimetres, the temperature of aqueous solution C is arranged on 40 DEG C and uses diameter to be that the Teflon stir oar of 13 centimetres stirs with the speed of 1200rpm simultaneously.Use peristaltic pump water solution A and aqueous solution B to be pumped into reactor with 0.7mL/ minute speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete.Water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 30 hours.Thereafter, through filtering, in the drying box of 100 DEG C, Cu is obtained after dry 10 hours
2+, Fe
3+doping sheet fluoridizes bismuth.
Embodiment 5: preparation 280mL consists of the water solution A of 10wt% bismuth nitrate, 0.3wt% copper nitrate, 0.2wt% ferric nitrate, 4wt% dust technology, 0.3wt% triethanolamine; Preparation 280mL consists of the ammonium fluoride of 30wt%, the aqueous solution B of 0.3wt% Tween-40; Preparation consists of the aqueous solution C of 0.3wt% perfluoroglutaric acid and 0.2wt% lauryl sulfosuccinic acid monoester disodium; Aqueous solution C is put into 2L volume, and internal diameter is 2/5 place to reactor cumulative volume in the cylindrical reactor of 20 centimetres, the temperature of aqueous solution C is arranged on 50 DEG C and uses diameter to be that the Teflon stir oar of 15 centimetres stirs with the speed of 1350rpm simultaneously.Use peristaltic pump water solution A and aqueous solution B to be pumped into reactor with 0.6mL/ minute speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete.Water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 30 hours.Thereafter, through filtering, in the drying box of 120 DEG C, Cu is obtained after dry 15 hours
2+, Fe
3+doping sheet fluoridizes bismuth.
Claims (2)
1. a liquid phase synthesis Cu
2+, Fe
3+doping sheet fluoridizes bismuth anode material for lithium-ion batteries and preparation method thereof, it is characterized in that preparing the water solution A 200-300mL consisting of 5-15wt% bismuth nitrate, 0.1-0.3wt% copper nitrate, 0.1-0.5wt% ferric nitrate, 1-5wt% dust technology, 0.1-0.5wt% auxiliary agent Z1, preparation consists of the ammonium fluoride of 15-45wt%, the aqueous solution B 200-300mL of 0.1-0.5wt% auxiliary agent Z2, water solution A is identical with the volume of aqueous solution B, and in aqueous solution B, the concentration of ammonium fluoride is 3 times of bismuth nitrate concentration in water solution A; Auxiliary agent Z3,0.1-0.5wt% of preparation 0.1-0.5wt% have the aqueous solution C of the auxiliary agent Z4 of cerium sulphate crystal effect; Aqueous solution C being put into volume is 2L, internal diameter is the 1/3-1/2 place to reactor cumulative volume in the cylindrical reactor of 15-20 centimetre, the temperature of aqueous solution C is arranged on 40-60 DEG C and uses Teflon stir oar to stir with the speed of 1200rpm-1500rpm simultaneously; Use peristaltic pump water solution A and aqueous solution B to be pumped into ad-hoc location in reactor with same speed simultaneously and until the water solution A of all preparations and the whole pump of aqueous solution B complete; The temperature of reactor is adjusted to 30-40 DEG C, maintain stir speed constant, reactor is placed in an atmospheric pressure volume ratio be 95: 5 nitrogen and hydrogen gas mixture keep 20-40 hour; Thereafter, through filtering, in the drying box of 100-150 DEG C, Cu is obtained after dry 10-20 hour
2+, Fe
3+doping sheet fluoridizes bismuth;
In preparation method as above, auxiliary agent Z1 is the one in monoethanolamine, triethanolamine, Triethanolammonium chloride; Auxiliary agent Z2 be mean molecule quantity at 10000-20000 polyvinyl alcohol, op-10, Tween-40; Auxiliary agent Z3 is the one in perfluoro-heptanoic acid, 2,2-difluoro cyclopropyl carboxylic acids, perfluoroglutaric acid; The auxiliary agent Z4 with cerium sulphate crystal effect is lauryl sulfosuccinic acid monoester disodium, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium, the one in Monododecylphosphate potassium;
In preparation method as above, the diameter of Teflon stir oar is less than the diameter of reactor 5 centimetres; The speed of peristaltic pump conveying water solution A and aqueous solution B is 0.1-1mL/ minute; Ad-hoc location as above refers to that water solution A enters entrance that the entrance of reactor and aqueous solution B enter reactor and is positioned at on the paddle axle circle that is the center of circle at same plane, and both line is through the center of circle and diameter is less than the diameter of paddle 1 centimetre.
2. liquid phase synthesis Cu according to claim 1
2+, Fe
3+doping sheet fluoridizes bismuth anode material for lithium-ion batteries and preparation method thereof, it is characterized in that the bismuth of fluoridizing prepared has more than 200mAh.g
-1specific capacity.
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| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| US20140284526A1 (en) * | 2013-03-21 | 2014-09-25 | Quantumscape Corporation | Method for forming metal fluoride material |
| CN104150543A (en) * | 2014-07-14 | 2014-11-19 | 宁波大学 | Cu<2+>, Ce<4+>, Ag<+> doped iron fluoride composite positive pole material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| US20140284526A1 (en) * | 2013-03-21 | 2014-09-25 | Quantumscape Corporation | Method for forming metal fluoride material |
| CN104150543A (en) * | 2014-07-14 | 2014-11-19 | 宁波大学 | Cu<2+>, Ce<4+>, Ag<+> doped iron fluoride composite positive pole material and preparation method thereof |
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