CN1686926A - Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat - Google Patents

Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat Download PDF

Info

Publication number
CN1686926A
CN1686926A CNA2005100116761A CN200510011676A CN1686926A CN 1686926 A CN1686926 A CN 1686926A CN A2005100116761 A CNA2005100116761 A CN A2005100116761A CN 200510011676 A CN200510011676 A CN 200510011676A CN 1686926 A CN1686926 A CN 1686926A
Authority
CN
China
Prior art keywords
lico
presoma
preparation
lithium
solid phase
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.)
Granted
Application number
CNA2005100116761A
Other languages
Chinese (zh)
Other versions
CN1269242C (en
Inventor
仇卫华
刘静静
于凌燕
赵海雷
李涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Tianjiao New Energy Co Ltd
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CNB2005100116761A priority Critical patent/CN1269242C/en
Publication of CN1686926A publication Critical patent/CN1686926A/en
Application granted granted Critical
Publication of CN1269242C publication Critical patent/CN1269242C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention provides a method for preparing LiCo1/3Ni1/3Mn1/3O2 material by adopting low-temperature solid-phase reaction, belonging to the field of lithium ion cell position electrode material preparation technology. Said invention utilizes two-step process to prepare precursor body, first step includes the following steps: uniformly mixing LiOH.H2O and H2C2O4 according to mixing ratio of 1:0.8-1.2; uniformly mixing acetates of Co, Ni and Mn according to the ratio of 1:1:1; and second step includes the following steps: ball-grinding and mixing the above-mentioned two materials, vacuum drying at 120-150 deg.C so as to obtain precursor body, roasting said precursor body for 6-15 hr at 500-800 deg.C so as to obtain finall product LiCo1/2Ni1/3Mn1/3O2.

Description

A kind of method that adopts low fever solid phase reaction to prepare laminar oxide material of lithium, cobalt, nickel and manganese
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, particularly provide a kind of employing low fever solid phase reaction to prepare LiCo 1-2x-yNi xMn xM yO 2The method of material, M is a metal, is used as anode material for lithium-ion batteries.
Technical background
In recent years, round the environmental protection in city and the research and development of power truck, for security and the price problem that solves lithium ion battery, people are carrying out the exploratory development of novel material always.And be widely used in the positive electrode material LiCoO of commodity lithium ion battery at present 2, because this material cost height overcharges unstable the reaching of status architecture and has certain safe new problem at the state of overcharging, so seek the main direction that the anodal equivalent material of super quality and competitive price becomes following lithium ion battery development.Stratiform LiMnO 2Have nontoxic, low-cost, energy density and theoretical capacity advantages of higher, the positive electrode material that is considered to have most development potentiality.But the synthesis condition harshness has limited its practical application.LiMnO 2Be a kind of metastable phase, structural instability in the electrochemistry working cycle changes spinel-like structural into when initial charge, and this transition process is irreversible.To the stratiform manganese behind its doping vario-property is that derivative has synthetic simple, low cost and other advantages, has caused that numerous scholars pay close attention to, and its application prospect is very good.Stratiform Li (Ni, Co, Mn) O 2In the material, by the Li (Ni of Ohzuku and Makimura proposition 1/3Co 1/3Mn 1/3) O 2Material, because its capacity height, the loop attenuation amount is little, can remedy LiCoO 2And LiMnO 2Deficiency, become and had most at present one of new type lithium ion battery positive electrode material of development prospect (T.Ohzuku, Y.Makimura, Chem.Lett.7 (2001): 642-643).
Present Li (Ni, Co, Mn) O 2The synthetic method of material adopts liquid-phase coprecipitation and high temperature solid-state method to synthesize substantially.Traditional high temperature solid state reaction synthesis temperature height, the time is long.As people (De-ChengLi, Takahisa Muta, Lian-Qi Zhang, et al.Effect of synthesis method on theelectrochemical performance of LiNi such as De-Cheng Li 1/3Co 1/3Mn 1/3O 2.Journal of Power Sources, 132 (2004): the 150-155) preparation method of employing solid phase synthesis, the acetate and the lithium acetate of cobalt nickel manganese are pressed stoichiometric, burn 400 ℃ after mixing in advance and obtain presoma, presoma is obtained Li (Ni at 900 ℃ of sintering 20h 1/3Co 13Mn 1/3) O 2Material.People (Jung-Min Kim, Hoon-Taek Chung.Thefirst cycle characteristics of Li[Ni such as Jung-Min Kim 1/3Co 1/3Mn 1/3] O 2Charged up to 4.7V.Electrochimica Acta, 49 (2004): 937-944) adopt LiOHH 2O, Ni (OH) 2, Co (NO 3) 26H 2O, Mn 3O 4As raw material, with ethanol mixing and ball milling after drying; Dried powder obtains final product at 950 ℃ of insulation 12h.People (Masaki Yoshio, Hideyuki Noguchi, et al.Preparation andproperties of LiCo such as Masaki Yoshio yMn xNi 1-x-yO 2As a) uses γ-MnOOH as the manganese source, and Co3O 4, LiOHH 2O, Ni (OH) 2After the mixing, grind with mortar; The mixture tablet forming obtains final product at 700-900 ℃ of sintering 20h.People (Zhangxiang Wang, Yucheng Sun, et al.Electrochemicalcharacterization of positive electrode material LiNi such as Zhaoxiang Wang 1/3Co 1/3Mn 1/3O 2Andcompatibility with electrolyte for lithium-ion batteries.Journal ofElectrochemical Society, 151 (6), 2004:A914-A921) use Ni 2O 3, Co 2O 3, MnO 2To a certain degree excessive LiOHH 2O mixes back sintering 24h in 850-1100 ℃ of temperature range, also can obtain intact laminate structure.
In article of delivering and patent, do not see at present the report that adopts with same raw materials of the present invention and synthetic this material of method as yet.
Summary of the invention
The object of the present invention is to provide a kind of employing low fever solid phase reaction to prepare LiCo 1-2x-yNi xMn xM yO 2The method of material has solved the synthetic LiCo of high temperature solid-state 1/3Ni 1/3Mn 1/3O 2Temperature height in the positive electrode material process, the time is long, the problem that energy consumption is high; Solve complex process in the liquid phase building-up process, multicomponent mixture is not easy by metering than sedimentary problem.
The present invention adopts the low fever solid phase reaction method, prepares presoma in two steps.The first step is respectively with lithium hydroxide (LiOH.H 2O) mixed in pulverizer 1~2 minute by stoichiometric ratio with oxalic acid (citric acid or sugar), its ratio is Li: H 2C 2O 4=1: 0.8~1.2; The acetate of cobalt nickel manganese was mixed in pulverizer 1~2 minute in proportion, mix, its ratio is Co: Ni: Mn=1: 1: 1.Second step was after two kinds of material ball millings that the first step mixes were mixed in 2~6 hours, 120~150 ℃ of vacuum-dryings, to prepare presoma.
Product preparation: the presoma for preparing was obtained final product in 6~12 hours 500~800 ℃ of roastings.
At preparation LiCo 1/3Ni 1/3Mn 1/3O 2Step in, can in the acetate of cobalt nickel manganese, add 0~0.1 mole Fe, V, acetate or the oxide compound of Cr, Al.Obtain final product LiCo 1-2x-yNi xMn xM yO 2, x=0.3~0.4 wherein, y=0~0.1.
The present invention adopts low fever solid phase reaction to prepare presoma, utilizes organic acid and LiOH.H earlier 2O forms the complex compound of lithium, and then with Ni, Co, Mn salt mix the formation presoma.
What people's such as the present invention and Yang Huo patent [publication number CN1461064A low fever solid phase reaction prepares lithium manganese oxide] was different is, our preparation be excessive component material, and adopt two-step approach to prepare the homogeneity that presoma more helps product.The method invention is simple to operate, and synthesis temperature is low, can reach the performance of liquid phase synthetic materials simultaneously.
Description of drawings
Fig. 1 is low-heat synthetic LiCo of the present invention 1/3Ni 1/3Mn 1/3O 2XRD figure, Fig. 1 (a) is by embodiment 1 preparation, and Fig. 1 (b) is by embodiment 2 preparations, and Fig. 1 (c) is by embodiment 3 preparations.
Fig. 2 is high temperature solid state reaction and liquid phase coprecipitation synthetic LiCo 1/3Ni 1/3Mn 1/3O 2XRD figure.Fig. 2 (a) high temperature solid-state is synthetic, and is synthetic by the method for Comparative Examples 1; Fig. 2 (b) liquid phase coprecipitation is synthetic, and is synthetic by the method for Comparative Examples 2.
Fig. 3 is low-heat synthetic LiCo of the present invention 1/3Ni 1/3Mn 1/3O 2Charging and discharging curve figure.Fig. 3 (a) is by the preparation of embodiment 1 method, and Fig. 3 (b) is prepared by embodiment 2 methods.Charging and discharging currents density 100mA/g, charging/discharging voltage scope 4.35-2.7V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 4 is high temperature solid state reaction and liquid phase coprecipitation synthetic LiCo 1/3Ni 1/3Mn 1/3O 2Charging and discharging curve figure.Fig. 4 (a) is prepared by Comparative Examples 1 method; Fig. 4 (b) is prepared by Comparative Examples 2 methods.Charging and discharging currents density 40mA/g, charging/discharging voltage scope 4.35-2.7V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 5 is low-heat synthetic LiCo of the present invention 1/3Ni 1/3Mn 1/3O 2Specific storage and cycle life figure with the Comparative Examples synthetic sample.X-coordinate is a cycle index, and ordinate zou is specific storage (mAh/g).The cycle performance contrast of 4 samples.
Embodiment
Further specify method of the present invention by the following examples.
1, preparation LiCo 1/3Ni 1/3Mn 1/3O 2
Execute example 1:
1) takes by weighing oxalic acid 12.67g and LiOHH respectively 2O4.417g becomes thick by 1: 1 mixed in molar ratio.
2) with (1: 1: the 1) weighing in molar ratio of cobaltous acetate (8.344g), nickelous acetate (8.464g), manganous acetate (8.252g), join 1 after mixing) in the powder that obtains, (Co+Ni+Mn): Li=1: 1.Grind and evenly obtain pink colour pasty state presoma.
3) pink colour pasty state presoma is taken out 150 ℃ of vacuum-drying 24h.
4) presoma is put into crucible oven, be warming up to 350 ℃ of insulation 4h, continue to be warming up to 700 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Embodiment 2:
1) takes by weighing citric acid 21.120g and LiOHH respectively 2O4.417g becomes thick by 1: 1 mixed in molar ratio.
2) with 2 in the example 1).
3) pink colour pasty state presoma takes out, 150 ℃ of vacuum-drying 24h.
4) presoma is put into crucible oven, be warming up to 400 ℃ of insulation 4h, continue to be warming up to 700 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Execute example 3:
1)-3) go on foot with embodiment 1,
4) presoma is put into crucible oven, be warming up to 350 ℃ of insulation 4h, continue to be warming up to 600 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Comparative Examples 1: high temperature solid-state is synthetic
The acetate of Ni, Co, Mn, Li is pressed the stoichiometric ratio mixing and ball milling, Ni: Co: Mn=1: 1: 1, (Ni+Co+Mn): Li=1: 1.Dried presoma is put into crucible oven, is warming up to 350 ℃ of insulation 4h with 5 ℃/min, continues to be warming up to 950 ℃, insulation 15h.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Comparative Examples 2: liquid phase coprecipitation is synthetic
Raw material adopts CoSO 47H 2O, NiSO 46H 2O, MnSO 4H 2O is made into certain density solution (0.1mol/0.4L) with metal sulfate, (Ni: Co: Mn)=1: 1: 1.Aforesaid liquid slowly is added drop-wise to the LiOHH of continuous stirring 2In the O solution (0.2mol/0.4L), control metallic solution and LiOHH 2The concentration of O solution, rate of addition (2-3s/ drips) and churning time (5.5h), continuous dripping alkali liquid (LiOH) (0.4mol/0.4L) is controlled between the pH value maintenance 13-14 of reaction solution in the reaction process.
After reaction finishes,, remove SO with deionized water repetitive scrubbing throw out 4 =Ion.The suction filtration gained is deposited in 120 ℃ of dry 12h down, with stoichiometric LiOHH 2Carry out pyroprocessing after O (1: the 1) mixing and ball milling.Sintering schedule is incubated 15h for be warming up to 600 ℃ of insulation 4h down with 5 ℃/min down at 900 ℃, carries out 600 ℃ of temper 6h then.
4 kinds of materials of above-mentioned synthetic are added conductive agent (10%) respectively, and the sticking film that is pressed into of binding agent (5%) is formed test cell with metallic lithium, carries out the constant current charge-discharge experiment.The battery charging and discharging electric current is 100mA/g among the embodiment 1,2, and the charging/discharging voltage scope is controlled between the 2.7-4.35V.The battery charging and discharging electric current is 40mA/g in the Comparative Examples 1,2, and the charging/discharging voltage scope is controlled between the 2.7-4.35V.
By the XRD figure of Fig. 1 and Fig. 2 as seen, five sample diffraction peak positions are consistent with the diffraction peak of R 3m spacer, illustrate to have formed good laminate structure.
By Fig. 3, Fig. 4 as seen, adopt the LiCo of low-heat solid phase synthesis process preparation 1/3Ni 1/3Mn 1/3O 2Material has more excellent performance, and the material that still can reach the liquid-phase synthesis process preparation when the 100mA/g constant current charge-discharge is at 40mA/g constant current charge-discharge identical specific storage and cycle performance.But the low-heat solid phase synthesis process is simple, low 200 ℃ of synthesis temperature.In 4 samples, the material property of high temperature solid state reaction preparation is the poorest, and specific storage only is 140mAh/g when the 40mA/g constant current charge-discharge.And decay is very fast.

Claims (3)

1, a kind of employing low fever solid phase reaction prepares LiCo 1/3Ni 1/3Mn 1/3O 2The method of material is characterized in that:
A, presoma preparation:
Prepare presoma in two steps, the first step is respectively with lithium hydroxide LiOH.H 2O and oxalic acid H 2C 2O 4Mix by stoichiometric ratio, its ratio is Li: H 2C 2O 4=1: 0.8~1.2; The acetate of cobalt nickel manganese is mixed in proportion, and its ratio is Co: Ni: Mn=1: 1: 1; Second step was after two kinds of material ball millings that the first step mixes were mixed in 2~6 hours, 120~150 ℃ of vacuum-dryings, to prepare presoma.
(b) preparation of product obtained final product LiCo with the presoma for preparing in 6~15 hours 500~800 ℃ of roastings 1/3Ni 1/3Mn 1/3O 2
2, require described preparation method according to right 1, it is characterized in that: replace oxalic acid with citric acid or sugar.
3, require described preparation method according to right 1 or 2, it is characterized in that: at preparation LiCo 1/3Ni 1/3Mn 1/3O 2Step in, in the acetate of cobalt nickel manganese, add 0~0.1 mole Fe, V, Cr, Al, acetate or the oxide compound of Li, obtain final product LiCo 1-2x-yNi xMn xM yO 2, wherein, x=0.3~0.4, y=0~0.1.
CNB2005100116761A 2005-04-30 2005-04-30 Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat Expired - Fee Related CN1269242C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100116761A CN1269242C (en) 2005-04-30 2005-04-30 Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100116761A CN1269242C (en) 2005-04-30 2005-04-30 Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat

Publications (2)

Publication Number Publication Date
CN1686926A true CN1686926A (en) 2005-10-26
CN1269242C CN1269242C (en) 2006-08-09

Family

ID=35304968

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100116761A Expired - Fee Related CN1269242C (en) 2005-04-30 2005-04-30 Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat

Country Status (1)

Country Link
CN (1) CN1269242C (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1330602C (en) * 2006-02-28 2007-08-08 济宁市无界科技有限公司 Lithium ion cell blended positive pole material and its preparing method
CN102163709A (en) * 2011-03-09 2011-08-24 合肥工业大学 Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof
CN101677125B (en) * 2008-09-16 2013-07-10 中国科学院福建物质结构研究所 Method for preparing layered cathode material of lithium ion battery
CN104362329A (en) * 2014-09-18 2015-02-18 长沙矿冶研究院有限责任公司 Method for preparing lithium-rich manganese-based layered lithium battery cathode material based on efficient solid-phase chemical complexation reaction

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102064317B (en) * 2009-11-13 2014-11-19 深圳市比克电池有限公司 LiFe1-xMxPO4 compound containing carbon element and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1330602C (en) * 2006-02-28 2007-08-08 济宁市无界科技有限公司 Lithium ion cell blended positive pole material and its preparing method
CN101677125B (en) * 2008-09-16 2013-07-10 中国科学院福建物质结构研究所 Method for preparing layered cathode material of lithium ion battery
CN102163709A (en) * 2011-03-09 2011-08-24 合肥工业大学 Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof
CN102163709B (en) * 2011-03-09 2013-01-09 合肥工业大学 Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof
CN104362329A (en) * 2014-09-18 2015-02-18 长沙矿冶研究院有限责任公司 Method for preparing lithium-rich manganese-based layered lithium battery cathode material based on efficient solid-phase chemical complexation reaction

Also Published As

Publication number Publication date
CN1269242C (en) 2006-08-09

Similar Documents

Publication Publication Date Title
CN110556536B (en) Six-element high-entropy oxide material for lithium ion battery and preparation method thereof
WO2023097982A1 (en) Compositve anode material, manufacturing method therefor, positive plate, and sodium ion battery
CN111170377B (en) Preparation method of lithium-rich manganese-based positive electrode material
CN108767239A (en) A kind of nickelic low cobalt tertiary cathode material and preparation method thereof
CN108448109B (en) Layered lithium-rich manganese-based positive electrode material and preparation method thereof
CN102306765A (en) Preparation method for nickel-manganese-cobalt anode material of lithium ion battery
CN103606667A (en) Preparation method for manganese solid solution anode material of lithium ion battery material
CN1767236A (en) Method for preparing lithium ion battery anode material LiMnxCoyNi1-x-yO2
CN104779385A (en) High-specific capacity lithium ion battery cathode material and preparation method thereof
CN103337615A (en) Positive pole material of high-capacity lithium ion battery and preparation method thereof
CN103606675A (en) Preparation method of metallic-ion-doped lithium-nickel-cobalt-oxygen positive pole material
CN103606669B (en) Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium
CN103178252A (en) Lithium ion battery anode material and preparation method thereof
CN102832387A (en) Layer-structured ternary material with rich lithium and high manganese as well as preparation method and application thereof
CN1269242C (en) Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat
CN103594703B (en) Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of bivalent cation
CN103594706B (en) Mix the preparation method of yttrium spinel lithium-rich lithium manganate cathode material
CN108598460A (en) A kind of anode material of lithium battery and preparation method thereof
CN103594704A (en) Preparation method for tetravalent titanium ion-doped spinel lithium-rich lithium manganate positive electrode material
CN1321881C (en) Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction
CN103594701B (en) Mix the preparation method of nickel spinel type lithium-rich lithium manganate cathode material
CN103594702B (en) The standby method of mixing the spinel lithium-rich lithium manganate cathode material of tin of double sintering legal system
CN105591098A (en) Li-rich positive electrode material with La doping and lithium amount change at same time and preparing method thereof
CN103066263A (en) Lithium ion battery positive material and preparation method thereof
CN103594700B (en) Mix the preparation method of the rich lithium manganate cathode material for lithium of vanadic spinel

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: SHENZHEN TIANJIAO TECHNOLOGY DEVELOPMENT CO., LTD.

Free format text: FORMER OWNER: BEIJING UNIVERSITY OF SCIENCE AND TECHNOLOGY

Effective date: 20100524

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 100083 NO.30 XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING TO: 518119 2/F, BUILDING A28, BENKANG INDUSTRIAL DISTRICT, KUIYONG STREET, LONGGANG DISTRICT, SHENZHEN CITY

TR01 Transfer of patent right

Effective date of registration: 20100524

Address after: 2, building 518119, A28 building, Ben Kang Industrial Zone, Kwai Chung street, Longgang District, Shenzhen

Patentee after: Tianjiao Tech Development Co., Ltd., Shenzhen City

Address before: 100083 Haidian District, Xueyuan Road, No. 30,

Patentee before: University of Science and Technology Beijing

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190428

Address after: 276000 Yan'an Road 119, Linyi Economic and Technological Development Zone, Shandong Province

Patentee after: Shandong Tianjiao new energy Co. Ltd.

Address before: 518119 2nd Floor, Building A28, Pengkang Industrial Zone, Kuiyong Street, Longgang District, Shenzhen

Patentee before: Tianjiao Tech Development Co., Ltd., Shenzhen City

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20060809

Termination date: 20200430

CF01 Termination of patent right due to non-payment of annual fee