CN101373829A - Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery - Google Patents

Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery Download PDF

Info

Publication number
CN101373829A
CN101373829A CNA2008102168020A CN200810216802A CN101373829A CN 101373829 A CN101373829 A CN 101373829A CN A2008102168020 A CNA2008102168020 A CN A2008102168020A CN 200810216802 A CN200810216802 A CN 200810216802A CN 101373829 A CN101373829 A CN 101373829A
Authority
CN
China
Prior art keywords
lithium
oxide
titanium
active material
substance
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
CNA2008102168020A
Other languages
Chinese (zh)
Other versions
CN101373829B (en
Inventor
岳敏
程林
贺雪琴
梅佳
张万红
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.)
BTR New Material Group Co Ltd
Original Assignee
Shenzhen BTR New Energy Materials Co Ltd
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 Shenzhen BTR New Energy Materials Co Ltd filed Critical Shenzhen BTR New Energy Materials Co Ltd
Priority to CN2008102168020A priority Critical patent/CN101373829B/en
Priority to PCT/CN2009/070353 priority patent/WO2010040285A1/en
Publication of CN101373829A publication Critical patent/CN101373829A/en
Application granted granted Critical
Publication of CN101373829B publication Critical patent/CN101373829B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a titanium cathode active substance, a preparation method thereof and a titanium lithium ion power battery, and aims to solve the technical problem of enhancing the rate performance of a lithium ion power battery. The formula of the titanium cathode active substance is Li4Ti5O12/Mx, wherein Li4Ti5O12 is spinel lithium titanate, M is a dopant such as a metal simple substance, a metal compound, a nonmetallic simple substance or a nonmetallic compound; the elements or the ions contained in the dopant enter the Li4Ti5O12 crystal lattice or are compounded with the Li4Ti5O12 crystal lattice; and the preparation method comprises the following steps: the precursor mixture of compound lithium titanate is prepared, and spray drying and heat treatment are performed. The cathode of the titanium lithium ion power battery adopts Li4Ti5O12/Mx. Compared with the prior art, the titanium cathode active substance has the advantages of high capacity, high bulk density, high volume specific capacity, good high-rate performance, good product uniformity, good battery processability, low possibility of air bulking of the battery, and low cost.

Description

Titanium is negative electrode active material and preparation method thereof, titanium based lithium-ion electrokinetic cell
Technical field
The present invention relates to the lithium ion battery cathode material and its preparation method that a kind of electrokinetic cell is used, and the lithium-ion-power cell that uses this negative material, particularly a kind of titanium is negative material and preparation method thereof, and to use this titanium be the lithium-ion-power cell of negative material.
Background technology
Along with the stable development of global economy, the output of automobile sharply increases.Fuel-engined vehicle institute exhaust gas discharged causes air environmental pollution, and airborne pollutant 63% comes from vehicle exhaust.Day by day the deterioration of environmental problem, particularly air quality has caused countries in the world, especially the common concern of developed country.After three the oil crisis outbursts in the whole world seventies in last century, each transnational motor corporation successively begins to research and develop various types of electric automobiles.Enter the nineties, along with the continuous intensification of global energy crisis, the harm of the exhaustion day by day of petroleum resources and air pollution, global warning aggravation begins to work out and progressively carry out severe automobile exhaust emission standard based on some western countries of USA and Europe.National governments and automobile enterprise generally recognize and reduce discharging to be the main direction of following automotive engineering development energy-conservation, the cleaning vehicle of developing no discharging or low emission, low oil consumption is imperative, the development and application of electric automobile will be the optimal path that solves these two technological difficulties, and low energy consumption, pollution-free green automobile begin to become the focus that people pay close attention to.
The used for electric vehicle electrokinetic cell that uses at present and develop mainly contains: lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery and fuel cell.Lithium ion battery be a kind ofly grow up in early 1990s, state-of-the-art rechargeable battery up to now.Lithium ion battery has the operating voltage height, is 3.6V, the energy density height, be respectively Cd/Ni and MH/Ni battery 3 times and 1.5 times, self discharge is little, less than 8%/month, long and memory-less effect of life-span, environment amenable advantage most possibly reaches the requirement of electric motor car.From Sony in 1991 the lithium-ion electric pool technology is introduced to the market so far, the progress of electrode material is promoting the continuous development of this technology always, and advanced electrode material becomes the core technology that present lithium ion battery updates.The lithium ion battery of prior art is used for electric motor car as electrokinetic cell, have following deficiency: it is very outstanding that (1) fills problem soon, automobile is when cruising, the discharge-rate of existing lithium ion battery can satisfy fully, but in braking procedure, braking procedure is of short duration, generally be no more than 10s, the immediate current that the motor demand is bigger, with effective braking and recuperated energy, automobile has 50～60% braking energy recyclable in theory, and the braking energy of actual recovered＜20%, discharge-rate, the especially rate of charge of existing lithium ion battery is difficult to reach the basic demand of electric automobile fast charging and discharging.(2) fail safe is that vehicle-mounted lithium ion battery moves towards practical key factor, the development of safety problem restriction electrokinetic cell, the prior art lithium ion battery is low with the positive and negative pole material fail safe, and mainly containing following four reason: a. tradition Li-Ion rechargeable battery positive electrode is LiCoO 2, graphite is negative material, positive electrode can decompose precipitated oxygen about 150 ℃, and reacts with electrolyte, causes the abnormal heating phenomenon; B. lithium ion is at the embedding current potential of the carbon-based material reduction potential near lithium metal; C. can not carry out high rate charge-discharge; D. not charging end indication on the voltage curve is not suitable for the electric vehicle electrokinetic cell.
As the lithium ion battery negative material, non-carbon negative pole material is subjected to researcher's attention day by day because of having high energy density and security performance.Non-material with carbon element lithium titanate Li 4Ti 5O 12Has spinel structure, space group Fd3m, during as negative material, little (cubical expansivity of graphite is generally about 9% for volume and structural change in the charge and discharge process, the variation repeatedly of temperature when discharging and recharging, cause smooth surface impaired easily, about useful life general 400 charge cycles), it is the zero strain material, thereby has a good cycle performance, the rough surface of lithium titanate anode can make cell charging times be up to 20,000 times, and its spinel structure is beneficial to the embedding of lithium ion and takes off, and voltage platform is positioned at 1.5V (vs.Li/Li +) near, be difficult for causing that lithium metal separates out, can carry out high current charge-discharge, solved the dendrite problem, battery unit can be avoided thermal runaway phenomenon.Different with common graphite, Li 4Ti 5O 12And can not form solid electrolyte interface SEI film on the interface between the electrolyte, therefore, internal resistance can not increase.Lithium titanate has tangible charge and discharge platform in addition, and discharging and recharging when finishing has tangible voltage jump, has good overcharging resisting performance and anti-mistake and puts performance.Because internal resistance is lower, can arrange in pairs or groups with different electrolyte, so the flash-over characteristic excellence under the low temperature.Spinel type lithium titanate is suitable for the electric vehicle electrical source of power, and its theoretical embedding lithium capacity is 175mAh/g, and actual specific capacity is between 120～130mAh/g.There is following deficiency in lithium titanate as negative material: 1, capacity is low, bulk density is low, compacted density is low, volume and capacity ratio is low; 2, the big high rate performance lifting of still needing; 3, homogeneity of product difference and battery poor processability; 4, easily suction, the easy inflatable of battery.
Summary of the invention
The purpose of this invention is to provide a kind of titanium is negative electrode active material and preparation method thereof, titanium based lithium-ion electrokinetic cell, and the technical problem that solve is to improve high rate performance, security performance, cycle life and the environmental-protecting performance of lithium-ion-power cell.
The present invention is by the following technical solutions: a kind of titanium is a negative electrode active material, and described titanium is that the general formula of negative electrode active material is Li 4Ti 5O 12/ M x, wherein: 0＜x≤10, Li 4Ti 5O 12Be spinel lithium titanate, M is dopant metal simple-substance, metallic compound, non-metal simple-substance or nonmetallic compound, and contained element of described dopant or ion enter Li 4Ti 5O 12Lattice dot matrix or compound with it; Titanium is negative electrode active material Li 4Ti 5O 12/ M xAverage grain diameter be 0.1～30 μ m; Described metal simple-substance is Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, metallic compound is an aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance is a boron, carbon, silicon, phosphorus or iodine, nonmetallic compound is furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber, cellulose; glucose; more than one of coal tar pitch or petroleum asphalt.
Li of the present invention 4Ti 5O 12/ M xMatrix is coated with the coating layer of nanometer clad material, and the nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material, and the thickness of coating layer is between 5～50nm.
A kind of titanium is the negative electrode active material preparation method, may further comprise the steps: one, press the lithium in the inorganic lithium salt: titanium dioxide: doping vario-property agent mol ratio 1.9～2.1:4.9～5.1: greater than 0～10 mixed composite lithium titanate precursor mixture that gets; Described inorganic lithium salt is a lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or lithium oxalate, the doping vario-property agent is a metal simple-substance, metallic compound, non-metal simple-substance or nonmetallic compound, described metal simple-substance is Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, metallic compound is an aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance is a boron, carbon, silicon, phosphorus or iodine, nonmetallic compound is furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber, cellulose; glucose; more than one of coal tar pitch or petroleum asphalt; Two, mixture is scattered in the organic solvent by mass ratio 1～1.5:1, spray-drying process under 100～350 ℃ of conditions obtains disperseing powder; Three, will disperse the programming rate of powder with 1～15 ℃/min, heat treatment is 4～40 hours in 500～950 ℃ temperature range, and naturally cooling to and obtaining titanium below 150 ℃ is negative electrode active material.
Method of the present invention is pressed the lithium in the inorganic lithium salt: titanium dioxide: the doping vario-property agent: nanometer clad material mol ratio 1.9～2.1:4.9～5.1: greater than 0～10: greater than 0～4.0 mixed composite lithium titanate precursor mixture that gets; The nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material.
Pulverize and sieve after the method for the present invention cooling, the titanium that obtains granularity and be 0.1～30 μ m is a negative electrode active material.
Method of the present invention is mixed the method that adopts with high-speed stirred or ball milling, and rotating speed 100～500r/min grinds and disperseed 2～40 hours.
Method organic solvent of the present invention is ethanol or acetone.
Feed argon gas or nitrogen during the method heat treatment of the present invention.
A kind of titanium based lithium-ion electrokinetic cell has positive pole and negative pole, and described negative pole is Li 4Ti 5O 12/ M x, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone form, mass ratio is 85～95%:3～10%:2～10%, wherein: 0＜x≤10, Li 4Ti 5O 12Be spinel lithium titanate, M is dopant metal simple-substance, metallic compound, non-metal simple-substance or nonmetallic compound, and contained element of described dopant or ion enter Li 4Ti 5O 12Lattice dot matrix or compound with it, average grain diameter are 0.1～30 μ m; Described metal simple-substance is Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, metallic compound is an aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance is a boron, carbon, silicon, phosphorus or iodine, nonmetallic compound is furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber, cellulose; glucose; more than one of coal tar pitch or petroleum asphalt.
The Li of battery of the present invention 4Ti 5O 12/ M xMatrix is coated with the coating layer of nanometer clad material, and the nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material, and the thickness of coating layer is between 5～50nm.
The just very iron system of battery of the present invention or manganese are that active material, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone are formed, and mass ratio is 85～95%:3～10%:2～10%.
The iron of battery of the present invention is that active material is LiFePO 4Or Li 2FeSiO 4, manganese is that active material is LiMnPO 4, LiCo xNi yMn (1-x-y)O 2, wherein 0≤x＜1,0≤y＜1, Li[Li xMn (2-x)] O 4, 0≤x＜1/3 wherein, Li[M xMn (2-x)] O 4, 0＜x＜1 wherein, M is the 3d transition metal, Li 2MnSiO 4
The iron system and the manganese of battery of the present invention are that active active material average grain diameter is 0.1～30 μ m.
The present invention compared with prior art, the element or the ion of dopant enter Li 4Ti 5O 12Lattice dot matrix, compound or surface doping, titanium is that negative electrode active material has the performance that capacity height, bulk density height, compacted density height, volume and capacity ratio height, big good rate capability, good product consistency, battery good processability and battery are difficult for inflatable, and it is with low cost, negative pole contains the titanium based lithium-ion electrokinetic cell that titanium is an active material, battery has higher safety performance, high rate performance, cycle performance, it is simple, with low cost to adopt the present invention to make battery methods; Battery is environmentally friendly, nothing is revealed, storage life is long, be easy to miniaturization, serviceability temperature is in extensive range, can be used as all kinds of electrokinetic cells.
Description of drawings
Fig. 1 is the SEM figure of the negative electrode active material that makes of the embodiment of the invention 1.
Fig. 2 is the discharge curve of the battery cell of the embodiment of the invention 1.
Fig. 3 is the cyclic curve figure of the battery cell of the embodiment of the invention 1.
Fig. 4 is the discharge curve of the LiFePO4/MCMB electrokinetic cell of Comparative Examples 1.
Fig. 5 is the cycle performance figure of the LiFePO4/MCMB electrokinetic cell of Comparative Examples 1.
Fig. 6 is the TEM figure of the negative electrode active material that makes of embodiment 1.
Fig. 7 is the XRD diffraction pattern of the negative electrode active material that makes of embodiment 1.
Fig. 8 is the XRD diffraction pattern of Comparative Examples 1 lithium titanate matrix.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.Titanium of the present invention is a negative electrode active material, and general formula is Li 4Ti 5O 12/ M x, wherein: 0＜x≤10, Li 4Ti 5O 12Be spinel lithium titanate, M is dopant metal simple-substance Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, the metallic compound aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance boron, carbon, silicon, phosphorus or iodine, the nonmetallic compound furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; more than one of coal tar pitch or petroleum asphalt, its contained element or ion enter Li 4Ti 5O 12Lattice dot matrix or compound with it, average grain diameter are 0.1～30 μ m.Li 4Ti 5O 12/ M xMatrix also can be coated with the coating layer of nanometer clad material outward, the nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material, and the thickness of coating layer is between 5～50nm.
Spinel lithium titanate Li 4Ti 5O 12Be the composite oxides of a kind of lithium metal and electronegative potential transition metals Ti, belong to AB 2X 4Series, its crystal structure and spinelle LiMn 2O 4Similar, can be written as Li[Li 1/3Ti 5/3] O 4, space group is Fd3m, has the three-dimensional diffusion passage of lithium ion.Wherein, O 2-Be positioned at 32e, constitute the FCC dot matrix, partial L i +Be positioned at tetrahedron 8a position, remaining Li +And Ti 4+Ratio with 1:5 is randomly dispersed in octahedra 16d position.Therefore, can it be described as Li according to structure 8a[Li 1/3Ti 5/3] 16d[O 4] 32eSpinel type lithium titanate does not have bulk strain in charge and discharge process, have long useful life, and this is because its discharge potential 1.55V (vs.Li/Li +) smooth, reactionless with electrolyte.
Titanium of the present invention is the negative electrode active material preparation method, may further comprise the steps:
One, presses lithium in the inorganic lithium salt: titanium dioxide: doping vario-property agent mol ratio 1.9～2.1:4.9～5.1: after mixing greater than 0～10, method with high-speed stirred or ball milling, rotating speed 100～500r/min grinds and disperses to make in 2～40 hours composite lithium titanate precursor mixture, i.e. Li 4Ti 5O 12With M xMixture, inorganic lithium salt is a lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or lithium oxalate, the doping vario-property agent is metal simple-substance Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn, Ge, the metallic compound aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride, magnesium fluoride, non-metal simple-substance boron, carbon, silicon, phosphorus, iodine and nonmetallic compound furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; more than one of coal tar pitch or petroleum asphalt; adopt the QM-1SP4 planetary ball mill of Nanjing Univ. Instrument Factory; can add and lithium simultaneously: titanium dioxide: the ratio of doping vario-property agent amount of substance is greater than 0～4.0 nanometer clad material, and the nanometer clad material is a nano titanium oxide; aluminium oxide; magnesium oxide; zirconia; cuprous oxide; silver oxide; tin oxide; acetylene black or nano-carbon material; Two, said mixture is scattered in organic solvent ethanol or the acetone, solid is 1～1.5:1 with the mass ratio ratio of organic solvent, adopt spray-dired method to make the dispersion powder, in the centrifugal spray granulating and drying machine of the big peak of the Wuxi City DFZR of drying equipment Co., Ltd type, spray-drying process under 100-350 ℃ of condition obtains disperseing powder; Three, will disperse the programming rate of powder with 1～15 ℃/min, heat treatment is 4～40 hours in 500～950 ℃ temperature range, during feed argon gas or nitrogen is made protection gas, make contained element of doping vario-property agent or ion enter Li 4Ti 5O 12Lattice dot matrix, compound naturally cools to below 150 ℃; Four, pulverize and sieve, the titanium that obtains granularity and be 0.1～30 μ m is a negative electrode active material.As being the doping vario-property agent with CuO, Mg, Al, F, C, finally obtaining forming expression formula is Li 4Ti 5O 12/ CuO 0.1(x=0.1), Li 4Ti 5O 12/ Al 0.2(x=0.2), Li 4Ti 5O 12/ Mg 0.3(x=0.3), Li 4Ti 5O 12/ F 0.05(x=0.05), Li 4Ti 5O 12/ C 10(x=10) titanium is a negative active core-shell material.
The KYKY-2800B type ESEM that adopts Beijing KYKY Technology Development Co., Ltd. is observed the surface topography of the material particle for preparing with method of the present invention, adopts X ' the Pert PRO diffractometer and the Japanese JEOL 2010 type transmission electron microscopes of Dutch PANalytical company to know that doped chemical or ion enter Li 4Ti 5O 12Lattice dot matrix and/or compound.
Titanium of the present invention is a negative electrode active material, in preparation process, mixes dopant, and dopant mainly is to replace Li[Li 1/3Ti 5/3] O 4In hexa-coordinate 16d site a part of material or play and disperse the coating effect, at spinel lithium titanate Li 4Ti 5O 12Do not find the diffraction maximum of alloy in the XRD figure of matrix, illustrate that foreign atom has entered lithium titanate Li 4Ti 5O 12In the lattice, enter Li at the element or the ion of dopant 4Ti 5O 12Under lattice dot matrix, the compound or surface coated effect, the capacity height of material, high conformity, good stability, good processability, the compacted density height of pole piece, good rate capability, energy density height, power density height, the high temperature performance of the battery of making as negative electrode active material of this material is good, security performance is good.
Titanium based lithium-ion electrokinetic cell of the present invention, negative pole is Li 4Ti 5O 12/ M x, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone form, mass ratio is 85～95%:3～10%:2～10%, wherein: 0＜x≤10.Just very iron system or manganese are that active material, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone are formed, and mass ratio is 85～95%:3～10%:2～10%.Fe is active anode compartment material: LiFePO 4Or Li 2FeSiO 4, Mn is active anode compartment material: LiMnPO 4, LiCo xNi yMn (1-x-y)O 2(0≤x＜1,0≤y＜1), Li[Li xMn (2-x)] O 4(0≤x＜1/3), Li[M xMn (2-x)] O 4(0＜x＜1, M is the 3d transition metal), Li 2MnSiO 4Fe system and Mn are that active anode compartment material average grain diameter is 0.1～30 μ m.Conductive agent is more than one of acetylene black, electrically conductive graphite, carbon nano-tube or carbon nano-fiber conductive materials, and binding agent is Kynoar PVDF or polytetrafluoroethylene.Electrolyte is for containing electrolyte LiPF 6, LiClO 4Or LiAsF 61mol/L organic solvent, organic solvent are more than one the mixed organic solvents among ethylene carbonate EC, propene carbonate PC, dimethyl carbonate DMC, diethyl carbonate DEC, dimethyl ether DME and the methyl ethyl carbonate EMC.Adopt Copper Foil and aluminium foil to be respectively negative pole and anodal collector, the co-polymer membrane of polypropylene screen, polyethylene film or propylene and ethene is a barrier film, and plastics, metal or alloy are battery case.
The manufacture method of titanium based lithium-ion electrokinetic cell of the present invention: with Li 4Ti 5O 12M x, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone be put in the DLH2 power mixer that Guangzhou good luck machinery plant produces, stir 12 hours required cathode sizes of acquisition with 150 rev/mins, cathode size is put on the tensile pulp machine, be coated on the Copper Foil of 20 μ m, 130 ℃ of bakings 6 hours, roll-in under the pressure of 10MPa is sheared according to the size of 270mm * 42.5mm, and being made into surface density is 230g/cm 2, compacted density is 2.1g/cm 3Cathode pole piece.With average grain diameter is the LiFePO of 2 μ m 4, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone be put in the DLH2 power mixer that Guangzhou good luck machinery plant produces, stirred 12 hours with 100 rev/mins of mixing speeds.Anode sizing agent is put on the tensile pulp machine, is coated on the aluminium foil of 20 μ m, 150 ℃ of bakings 6 hours, roll-in under the pressure of 25MPa was sheared according to the size of 320mm * 41.5mm, and being made into surface density is 210g/cm 2Anode pole piece.Anode pole piece, barrier film and cathode pole piece are superimposed in order, on the 423048 type up-coilers of Shaoyang Dali Power Sources Co., Ltd., reel, in the shell of packing into after the hot pressing.Battery cell is put into Shanghai medical equipment manufactory produces in the DZF-6050 hollow baking box,, again battery cell is transferred between fluid injection, inject 1mol/L LiPF 80 ℃ of following vacuum bakeouts 24 hours 6Electrolyte, promptly be made into battery cell after the sealing.According to needed voltage and current,, take mode in parallel and that series connection combines to be assembled into electrokinetic cell with battery cell.
With the battery cell for preparing, place after 12 hours, be put into battery and change into cashier's office in a shop, charging current multiplying power 1.0C is charged to 3.0V, and carrying out constant voltage charge to electric current is 0.01C, with 1.0C discharge-rate constant-current discharge, discharge cut-off voltage is 1.0V then, repeats to discharge and recharge 2 times.With internal resistance, capacity, the open-circuit cell data of the BS-8303Q of Qingtian Industry Co., Ltd., Guangzhou battery test system test battery monomer, the charging and discharging curve and the cycle performance of while test battery monomer.Test condition is as follows: charging current multiplying power 1.0C, be charged to 3.0V, and carrying out constant voltage charge to electric current is 0.01C, with 1.0C discharge-rate constant-current discharge, discharge cut-off voltage is 1.0V.
Embodiment 1: with the nanoscale cupric oxide powder of 2mol lithium carbonate, 5mol titanium dioxide, 0.1mol, and nano-sized carbon 4mol, rotating speed 300r/min grinds and disperses to make in 16 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.5:1, obtains disperseing powder with spray drying under 150 ℃ of conditions; To disperse the programming rate of powder with 5 ℃/min, heat treatment is 24 hours in 700 ℃ temperature range, during feed nitrogen, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that particle mean size is 10 μ m 4Ti 5O 12/ CuO 0.1(x=0.1) negative electrode active material.As shown in Figure 1, lithium titanate material has the microscopic feature of spherical and class sphere, smooth surface, as shown in Figure 6, the about 8nm of the thickness of nanometer coating layer, the coating layer uniformity, as shown in Figure 7, XRD figure shows, the assorted peak of copper does not appear in the collection of illustrative plates comprising, illustrate that dopant has entered the lattice of spinel type lithium titanate, coating layer is that unbodied carbon and phosphorus content are lower, shows not obvious on the XRD figure spectrum.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 90%:5%:5% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 90%:5%:5% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.As shown in Figure 2,5C discharge-rate discharge capacity is 2.0Ah, and capacity still is 1.1Ah under the condition of discharge-rate 30C, and as shown in Figure 3, under the 10C discharge-rate condition, the cycle performance of battery is very desirable, and the capability retention in 2000 weeks is 98.1%.
Embodiment 2: with the nano-alumina powder end of 2.1mol lithium carbonate, 5.1mol titanium dioxide, 0.1mol, rotating speed 200r/min grinds and disperses to make in 24 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.5:1, obtains disperseing powder with spray drying under 250 ℃ of conditions; To disperse the programming rate of powder with 10 ℃/min, heat treatment is 40 hours in 400 ℃ temperature range, during feed nitrogen, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that particle mean size is 1 μ m 4Ti 5O 12/ (Al 2O 3) 0.1(x=0.1) negative electrode active material.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 85%:10%:5% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 90%:4%:6% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.
Embodiment 3, and with nano-alumina powder end, the 2mol acetylene black of 2.0mol lithium carbonate, 4.95mol titanium dioxide, 0.1mol, rotating speed 100r/min grinds and disperses to make in 24 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.0:1, obtains disperseing powder with spray drying under 350 ℃ of conditions; To disperse the programming rate of powder with 15 ℃/min, heat treatment is 4 hours in 950 ℃ temperature range, during feed nitrogen, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that granularity is 1 μ m 4Ti 5O 12/ (Al 2O 3) 0.1(x=0.1) negative electrode active material.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 95%:3%:2% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 95%:3%:2% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.
Embodiment 4, with the nanoscale Zirconium oxide powder of 1.9mol lithium carbonate, 4.9mol titanium dioxide, 0.1mol, and the 0.4mol nano-sized carbon, rotating speed 500r/min grinds and disperses to make in 2 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and solid is 1.2:1 with the volume of organic solvent ratio, obtains disperseing powder with spray drying under 350 ℃ of conditions; To disperse the programming rate of powder with 10 ℃/min, heat treatment is 24 hours in 700 ℃ temperature range, during feed nitrogen, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that granularity is 1 μ m 4Ti 5O 12/ (ZrO 2) 0.1(x=0.1) negative electrode active material.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 85%:5%:10% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 90%:5%:5% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.
Embodiment 5, and with the nanoscale aluminum fluoride powder of 2.0mol lithium carbonate, 5mol titanium dioxide, 0.1mol, rotating speed 100r/min grinds and disperses to make in 40 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.3:1, obtains disperseing powder with spray drying under 100 ℃ of conditions; To disperse the programming rate of powder with 8 ℃/min, heat treatment is 30 hours in 600 ℃ temperature range, during feed argon gas, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that granularity is 1 μ m 4Ti 5O 12/ (AlF 3) 0.1(x=0.1) negative electrode active material.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 85%:5%:10% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 95%:3%:2% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.
Example 6, with the nano-alumina powder end of 2.0mol lithium carbonate, 5mol titanium dioxide, 10mol, rotating speed 100r/min grinds and disperses to make in 40 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.5:1, obtains disperseing powder with spray drying under 100 ℃ of conditions; To disperse the programming rate of powder with 8 ℃/min, heat treatment is 30 hours in 600 ℃ temperature range, during feed argon gas, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that granularity is 1 μ m 4Ti 5O 12/ (Al 2O 3) 10(x=10) negative electrode active material.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 85%:5%:10% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 85%:10%:5% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.
Embodiment 7, and with the nanoscale aluminum fluoride powder of 2.0mol lithium carbonate, 5mol titanium dioxide, 0.1mol, rotating speed 100r/min grinds and disperses to make in 40 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.3:1, obtains disperseing powder with spray drying under 100 ℃ of conditions; To disperse the programming rate of powder with 1 ℃/min, heat treatment is 30 hours in 500 ℃ temperature range, during feed argon gas, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that granularity is 1 μ m 4Ti 5O 12/ (AlF 3) 0.1(x=0.1) negative electrode active material.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 85%:5%:10% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 85%:5%:10% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.
Comparative Examples 1, with 2.0mol lithium carbonate, 5mol titanium dioxide, rotating speed 300r/min grinds and disperses to make in 24 hours the composite lithium titanate precursor mixture; The composite lithium titanate precursor mixture is scattered in the ethanol, and the ratio of solid and organic solvent is 1.5:1, obtains disperseing powder with spray drying under 150 ℃ of conditions; To disperse the programming rate of powder with 10 ℃/min, heat treatment is 30 hours in 700 ℃ temperature range, during feed nitrogen, naturally cool to below 150 ℃; Pulverize and sieve, obtain the Li that granularity is 1 μ m 4Ti 5O 12Negative electrode active material.As shown in Figure 8, except the diffraction maximum of spinel type lithium titanate, do not have other the assorted peak of diffraction, and the intensity of diffraction maximum is higher in the collection of illustrative plates.
With above-mentioned gained negative active core-shell material, conductive agent acetylene black and binding agent PVDF, be that 85%:5%:10% makes cathode pole piece by mass ratio.With LiFePO 4, conductive agent acetylene black and binding agent PVDF, be that 95%:3%:2% makes anode pole piece by mass ratio.Anode pole piece, Celgard2400 type polypropylene diaphragm and cathode pole piece are superimposed in order, and in the plastic casing of packing into after coiling, the hot pressing, it is LiPF that the 1mol/L electrolyte is injected in the baking back 6, the electrolyte of solvent EC+DMC volume ratio 1:1 promptly is prepared into the electrokinetic cell monomer after the sealing.
With the electrokinetic cell monomer for preparing, test test result such as table 1 after changing into.Cycle performance as shown in Figure 5, the capability retention in 1500 weeks is 92%.
Comparative Examples 2, as positive active material, MCMB is a negative electrode active material with present business-like LiFePO4, is assembled into LiFePO4/MCMB lithium-ion-power cell according to the technology of maturation, test condition: at upper and lower limit voltage is 2.5-4.1V, discharges and recharges 3 times with the electric current of 0.1C.The discharge curve of different multiplying as shown in Figure 4, under the 0.2C discharge-rate condition, discharge capacity is 487mAh, the discharge-rate of 50C is about 360mAh.
With the electrokinetic cell monomer for preparing, test after changing into, test result such as table 1, cycle performance as shown in Figure 5, the capability retention in 500 weeks is 88%.
Table 1 embodiment and Comparative Examples electrokinetic cell monomer test result
Figure A200810216802D00211
As can be seen from Table 1, adopt the lithium titanate of doping vario-property preparation, adopt the not Comparative Examples of the lithium titanate of doping vario-property preparation, the high rate performance of battery is significantly increased, and the lithium titanate of doping vario-property preparation is good active material.
In an embodiment, inorganic lithium salt has only been enumerated lithium carbonate, lithium carbonate be lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 and lithium oxalate are lithium-containing compounds, the character that in the technology that obtains the composite lithium titanate precursor mixture, has the reaction of heating and decomposition and titanium dioxide, so lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 and lithium oxalate all are suitable for method of the present invention.
In an embodiment, aluminium oxide has only been enumerated in the doping vario-property agent, zirconia, cupric oxide and aluminum fluoride, aluminium oxide, zirconia, cupric oxide, aluminum fluoride and metal simple-substance Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn, Ge, metallic compound magnesium oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, lithium fluoride, magnesium fluoride, non-metal simple-substance boron, carbon, silicon, phosphorus, iodine and nonmetallic compound furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch or petroleum asphalt; all be carbon compound; resolve into amorphous carbon in the technology that obtains the composite lithium titanate precursor mixture, its contained element or ion enter Li 4Ti 5O 12Lattice dot matrix or compound with it, all can improve the chemical property of material, so metal simple-substance Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn, Ge, metallic compound magnesium oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, lithium fluoride, magnesium fluoride, non-metal simple-substance boron, carbon, silicon, phosphorus, iodine and nonmetallic compound furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch or petroleum asphalt all is suitable for method of the present invention.
In an embodiment, the nanometer clad material has only been enumerated acetylene black, nano-sized carbon, and acetylene black, nano-sized carbon and nano titanium oxide, aluminium oxide, magnesium oxide, zirconia are ion conductors, can increase conductivity of electrolyte materials behind the formation coating layer, improves high rate performance.Cuprous oxide, silver oxide, tin oxide form the electrode potential that coating layer can change lithium titanate, so nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, all are suitable for the present invention.
Titanium based lithium-ion electrokinetic cell of the present invention has the necessary characteristic of lithium ion battery of future generation, charging times More and charging process is faster, with lithium titanate during as the negative material of lithium ion battery, can improve system Fast charging and discharging and cycle performance, charging and discharging curve significantly discharge and recharge sign, and security performance improves, Be suitable as the electrical source of power of electric motor car.
Battery of the present invention has higher security performance, good high rate performance, long cycle life and High gravimetric specific energy, and make simply, with low cost, can replace now widely used plumbic acid and hold Battery. High-energy, high power have the electrical source of power of good high rate performance and cycle performance, to replace Traditional lead-acid accumulator. Simultaneously, the novel battery that the present invention relates to is environmentally friendly, is a kind of green ring Protect battery. And, battery of the present invention have do not have to reveal, storage life is long, be easy to the advantage such as miniaturization, And serviceability temperature is in extensive range.

Claims (13)

1. a titanium is a negative electrode active material, it is characterized in that: described titanium is that the general formula of negative electrode active material is Li 4Ti 5O 12/ M x, wherein: 0＜x≤10, Li 4Ti 5O 12Be spinel lithium titanate, M is dopant metal simple-substance, metallic compound, non-metal simple-substance or nonmetallic compound, and contained element of described dopant or ion enter Li 4Ti 5O 12Lattice dot matrix or compound with it; Titanium is negative electrode active material Li 4Ti 5O 12M xAverage grain diameter be 0.1～30 μ m; Described metal simple-substance is Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, metallic compound is an aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance is a boron, carbon, silicon, phosphorus or iodine, nonmetallic compound is furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber, cellulose; glucose; more than one of coal tar pitch or petroleum asphalt.
2. titanium according to claim 1 is a negative electrode active material, it is characterized in that: described Li 4Ti 5O 12/ M xMatrix is coated with the coating layer of nanometer clad material, and the nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material, and the thickness of coating layer is between 5～50nm.
3. a titanium is the negative electrode active material preparation method, may further comprise the steps: one, press the lithium in the inorganic lithium salt: titanium dioxide: doping vario-property agent mol ratio 1.9～2.1:4.9～5.1: greater than 0～10 mixed composite lithium titanate precursor mixture that gets; Described inorganic lithium salt is a lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or lithium oxalate, the doping vario-property agent is a metal simple-substance, metallic compound, non-metal simple-substance or nonmetallic compound, described metal simple-substance is Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, metallic compound is an aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance is a boron, carbon, silicon, phosphorus or iodine, nonmetallic compound is furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber, cellulose; glucose; more than one of coal tar pitch or petroleum asphalt; Two, mixture is scattered in the organic solvent by mass ratio 1～1.5:1, spray-drying process under 100～350 ℃ of conditions obtains disperseing powder; Three, will disperse the programming rate of powder with 1～15 ℃/min, heat treatment is 4～40 hours in 500～950 ℃ temperature range, and naturally cooling to and obtaining titanium below 150 ℃ is negative electrode active material.
4. titanium according to claim 3 is the negative electrode active material preparation method, it is characterized in that: the described lithium of pressing in the inorganic lithium salt: titanium dioxide: doping vario-property agent: nanometer clad material mol ratio 1.9～2.1:4.9～5.1: greater than 0～10: greater than 0～4.0 mixed composite lithium titanate precursor mixture that gets; The nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material.
5. be the negative electrode active material preparation method according to claim 3 or 4 described titaniums, it is characterized in that: pulverize and sieve after the described cooling, the titanium that obtains granularity and be 0.1～30 μ m is a negative electrode active material.
6. titanium according to claim 5 is the negative electrode active material preparation method, it is characterized in that: the method with high-speed stirred or ball milling is adopted in described mixing, and rotating speed 100～500r/min grinds and disperseed 2～40 hours.
7. titanium according to claim 6 is the negative electrode active material preparation method, it is characterized in that: described organic solvent is ethanol or acetone.
8. titanium according to claim 7 is the negative electrode active material preparation method, it is characterized in that: feed argon gas or nitrogen during the described heat treatment.
9. a titanium based lithium-ion electrokinetic cell has positive pole and negative pole, it is characterized in that: described negative pole is Li 4Ti 5O 12/ M x, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone form, mass ratio is 85～95%:3～10%:2～10%, wherein: 0＜x≤10, Li 4Ti 5O 12Be spinel lithium titanate, M is dopant metal simple-substance, metallic compound, non-metal simple-substance or nonmetallic compound, and contained element of described dopant or ion enter Li 4Ti 5O 12Lattice dot matrix or compound with it, average grain diameter are 0.1～30 μ m; Described metal simple-substance is Al, Mg, Cu, Ag, Ni, Co, Mn, Cd, Pb, Bi, Sn or Ge, metallic compound is an aluminium oxide, magnesium oxide, zirconia, cupric oxide, cuprous oxide, silver oxide, cobalt oxide, manganese dioxide, manganese sesquioxide managnic oxide, lead oxide, tin oxide, aluminum fluoride, lithium fluoride or magnesium fluoride, non-metal simple-substance is a boron, carbon, silicon, phosphorus or iodine, nonmetallic compound is furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber, cellulose; glucose; more than one of coal tar pitch or petroleum asphalt.
10. titanium based lithium-ion electrokinetic cell according to claim 9 is characterized in that: described Li 4Ti 5O 12M xMatrix is coated with the coating layer of nanometer clad material, and the nanometer clad material is nano titanium oxide, aluminium oxide, magnesium oxide, zirconia, cuprous oxide, silver oxide, tin oxide, acetylene black or nano-carbon material, and the thickness of coating layer is between 5～50nm.
11. according to claim 9 or 10 described titanium based lithium-ion electrokinetic cells, it is characterized in that: described just very iron system or manganese are that active material, conductive agent and the binding agent that is dissolved in the N-methyl pyrrolidone are formed, and mass ratio is 85～95%:3～10%:2～10%.
12. titanium based lithium-ion electrokinetic cell according to claim 11 is characterized in that: described iron is that active material is LiFePO 4Or Li 2FeSiO 4, manganese is that active material is LiMnPO 4, LiCo xNi yMn (1-x-y)O 2, wherein 0≤x＜1,0≤y＜1, Li[Li xMn (2-x)] O 4, 0≤x＜1/3 wherein, Li[M xMn (2-x)] O 4, 0＜x＜1 wherein, M is the 3d transition metal, Li 2MnSiO 4
13. titanium based lithium-ion electrokinetic cell according to claim 12 is characterized in that: described iron system and manganese are that active active material average grain diameter is 0.1～30 μ m.
CN2008102168020A 2008-10-07 2008-10-07 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery Active CN101373829B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2008102168020A CN101373829B (en) 2008-10-07 2008-10-07 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery
PCT/CN2009/070353 WO2010040285A1 (en) 2008-10-07 2009-02-04 Titanium-containing active material for negative electrodes and its production method and titanium-containing power lithium battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008102168020A CN101373829B (en) 2008-10-07 2008-10-07 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery

Publications (2)

Publication Number Publication Date
CN101373829A true CN101373829A (en) 2009-02-25
CN101373829B CN101373829B (en) 2011-05-11

Family

ID=40447851

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008102168020A Active CN101373829B (en) 2008-10-07 2008-10-07 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery

Country Status (2)

Country Link
CN (1) CN101373829B (en)
WO (1) WO2010040285A1 (en)

Cited By (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010040285A1 (en) * 2008-10-07 2010-04-15 深圳市贝特瑞新能源材料股份有限公司 Titanium-containing active material for negative electrodes and its production method and titanium-containing power lithium battery
CN101800305A (en) * 2010-03-09 2010-08-11 福建师范大学 Method for depositing silicon film at surface of lithium titanate cathode of lithium ion battery
CN101800306A (en) * 2010-03-25 2010-08-11 陕西师范大学 Method for preparing tin oxide/carbon composite electrode material for lithium-ion batteries
CN101841017A (en) * 2009-03-16 2010-09-22 中国科学院成都有机化学有限公司 Lithium titanate/carbon/carbon nano tube composite electrode material and preparation method thereof
CN101859890A (en) * 2010-06-21 2010-10-13 惠州市赛能电池有限公司 Anode material of lithium ion battery
CN101609883B (en) * 2009-07-13 2011-01-05 北京安华联合能源科技有限责任公司 Preparation method of nano-silver particle dispersed Li4Ti5O12 thin film lithium ion battery negative electrode
CN101540392B (en) * 2009-04-09 2011-04-06 西安建筑科技大学 Method for preparing lithium-manganese silicate of cathode material of lithium-ion battery
CN102013479A (en) * 2010-10-19 2011-04-13 合肥国轩高科动力能源有限公司 Method for preparing carbon-encapsulated zirconium-doped lithium titanium as lithium ion battery cathode material
CN102024574A (en) * 2010-12-20 2011-04-20 浙江吉利汽车研究院有限公司 Method for preparing composite anode material of super capacitor lithium titanate
CN102122708A (en) * 2010-01-08 2011-07-13 中国科学院物理研究所 Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole
CN102201570A (en) * 2010-03-25 2011-09-28 清华大学 Preparation method for electrode material of lithium battery
CN102299297A (en) * 2011-07-30 2011-12-28 珠海锂源动力科技有限公司 Cathode of lithium ion battery and preparation method thereof
CN102414883A (en) * 2009-04-24 2012-04-11 夏普株式会社 Positive active material and nonaqueous secondary battery equipped with positive electrode including same
CN102442695A (en) * 2010-10-09 2012-05-09 合肥国轩高科动力能源有限公司 Preparation method of lithium titanate material of lithium ion battery
CN102544465A (en) * 2010-12-20 2012-07-04 财团法人工业技术研究院 Phosphorus-doped spinel-structured lithium titanium oxide material and preparation method thereof
CN102544438A (en) * 2010-12-20 2012-07-04 梅岭化工厂 Lithium titanate electrode doped with nanometer silver powder for lithium ion battery and preparation method for electrode
CN102623698A (en) * 2012-04-16 2012-08-01 南京大学 Titanium lithium silicate, preparation method thereof and use of the same serving as electrode material of lithium battery
CN102637873A (en) * 2012-03-27 2012-08-15 中宇锂电能源股份有限公司 Lithium ion battery cathode material and method for preparing same
CN102013527B (en) * 2009-09-08 2012-08-29 清华大学深圳研究生院 Rechargeable zinc ion battery
CN102683664A (en) * 2012-05-17 2012-09-19 湖南瑞翔新材料股份有限公司 Lithium titanate negative electrode material and preparation method thereof
CN102683663A (en) * 2012-05-07 2012-09-19 宁德新能源科技有限公司 Lithium-ion secondary battery and anode material and manufacturing method thereof
US20120270105A1 (en) * 2011-04-20 2012-10-25 Goto Natsumi Nonaqueous electrolyte secondary battery
CN102869612A (en) * 2010-04-28 2013-01-09 石原产业株式会社 Novel lithium titanate, method for producing same, electrode active material containing the lithium titanate, and electricity storage device using the electrode active material
CN102867948A (en) * 2011-07-05 2013-01-09 三星Sdi株式会社 Composite, method of manufacturing the composite, anode active material including the composite, anode including the anode active material, and lithium secondary battery including the anode
CN102891304A (en) * 2012-09-24 2013-01-23 合肥国轩高科动力能源有限公司 Lithium titanate and lithium ion battery using lithium titanate as anode active substance
CN101877407B (en) * 2009-04-30 2013-06-19 比亚迪股份有限公司 Cathode active material, preparation method thereof and battery
CN103178253A (en) * 2011-12-26 2013-06-26 太阳诱电株式会社 Lithium-titanium complex oxide, and battery electrode and lithium ion secondary battery containing same
TWI403017B (en) * 2010-04-27 2013-07-21 Hon Hai Prec Ind Co Ltd Method for making electrode material of lithium-ion batteries
CN103259048A (en) * 2013-05-22 2013-08-21 南京双登科技发展研究院有限公司 Formation method for prolonging cycle life of lithium titanate battery
CN103280567A (en) * 2013-03-06 2013-09-04 广州市东力电池实业有限公司 Li4Ti5O12 having surface chemically plated by metal, and preparation method thereof
CN103337616A (en) * 2013-06-28 2013-10-02 上海电力学院 Metal oxide coated lithium titanate negative pole material and preparation method thereof
CN103384931A (en) * 2010-12-23 2013-11-06 野猫技术开发公司 Lithium-ion battery materials with improved properties
CN103390746A (en) * 2012-05-07 2013-11-13 电子科技大学 Method for improving performance of lithium ion battery cathode material lithium titanate
CN103779549A (en) * 2012-10-18 2014-05-07 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion batteryelectrode material nano lithium titanate with uniformly-dispersed particles
CN103840146A (en) * 2012-11-27 2014-06-04 西安物华新能源科技有限公司 Preparation method of high-tap-density lithium titanate material
CN103872305A (en) * 2014-03-24 2014-06-18 四川兴能新材料有限公司 Preparation method of polyelectrolyte coated Li4Ti5O12 negative electrode material
CN103872304A (en) * 2014-03-18 2014-06-18 中国科学院化学研究所 Novel magnesium secondary battery electrode material and application thereof
US8765213B2 (en) 2010-02-06 2014-07-01 Tsinghua University Method for making lithium-ion battery electrode material
CN104009218A (en) * 2014-05-07 2014-08-27 上海应用技术学院 Preparation method of tin/lithium titanate composite electrode material as lithium ion battery negative electrode material
CN104037400A (en) * 2014-07-09 2014-09-10 扬州大学 Preparation method of copper-doped lithium titanate lithium ion battery cathode material
CN104091917A (en) * 2014-07-10 2014-10-08 上海电力学院 Titanic oxide negative electrode material used as sodium-ion battery and preparation method of thereof
TWI458164B (en) * 2010-03-30 2014-10-21 Hon Hai Prec Ind Co Ltd Method for making electrode material of lithium-ion battery
TWI471270B (en) * 2009-05-26 2015-02-01 Ishihara Sangyo Kaisha Lithium titanate, method for preparing the same, and electrode active material and storage device using the same
CN104347864A (en) * 2013-08-05 2015-02-11 神华集团有限责任公司 Material and preparation thereof, lithium ion battery electrode active substance containing material, electrode material, electrode and battery
CN104577130A (en) * 2014-12-13 2015-04-29 山东神工海特电子科技有限公司 Flexible-packaged high-power lithium iron phosphate power battery
WO2015067136A1 (en) * 2013-11-11 2015-05-14 江苏华东锂电技术研究院有限公司 Active material for negative electrode of lithium ion battery and preparation method therefor, and lithium ion battery
CN104966828A (en) * 2015-08-07 2015-10-07 田东 Preparation method of high-capacity lithium battery negative electrode material
CN104979542A (en) * 2014-04-11 2015-10-14 上海杉杉科技有限公司 Modified lithium titanate composite material, preparation method and application thereof
CN105006555A (en) * 2015-08-07 2015-10-28 田东 Preparation method of compound lithium titanate anode material doped with metallic tin
CN105185972A (en) * 2014-05-27 2015-12-23 中信国安盟固利动力科技有限公司 Composite titanate negative electrode material of lithium ion secondary battery and synthetic method thereof
WO2016141861A1 (en) * 2015-03-06 2016-09-15 苏州宝时得电动工具有限公司 Battery, battery pack and uninterruptible power supply
CN105958021A (en) * 2016-05-27 2016-09-21 天津泰和九思科技有限公司 Lithium titanate composite material and preparation method thereof and lithium-ion battery
CN105990574A (en) * 2015-02-11 2016-10-05 微宏动力系统（湖州）有限公司 Coated lithium-rich negative electrode material and preparation method thereof
WO2016165390A1 (en) * 2015-04-15 2016-10-20 田东 Preparation method for modified lithium titanate negative electrode material
WO2016192541A1 (en) * 2015-06-05 2016-12-08 田东 Method for manufacturing multiphase metal doped lithium titanate negative electrode material
CN106935831A (en) * 2017-03-31 2017-07-07 深圳市国创新能源研究院 A kind of lithium titanate anode material for suppressing flatulence and its preparation method and application
CN106935829A (en) * 2017-03-30 2017-07-07 上海动力储能电池系统工程技术有限公司 A kind of method for strengthening lithium ion battery lithium titanate material low-temperature characteristics
CN107634221A (en) * 2017-08-18 2018-01-26 华北理工大学 A kind of synthetic method for the ferrous silicate lithium anode material that bismuth doping is prepared using iron tailings as raw material
CN107732172A (en) * 2017-09-25 2018-02-23 中国计量大学 A kind of lithium ion battery negative material and preparation method thereof
CN107994219A (en) * 2017-11-27 2018-05-04 桑顿新能源科技有限公司 A kind of metal-doped composite positive pole of graphene coated and preparation method thereof
CN108365194A (en) * 2018-02-06 2018-08-03 深圳市普锐能源科技有限公司 A kind of preparation method of composite negative electrode material of lithium ion battery
CN108417785A (en) * 2018-01-11 2018-08-17 茆胜 Fluorine nitrogen-doped graphene coats lithium titanate composite material and preparation method thereof
CN108682832A (en) * 2018-06-11 2018-10-19 四会市恒星智能科技有限公司 Lithium battery composite negative pole material and preparation method thereof
CN108695494A (en) * 2018-04-25 2018-10-23 福建翔丰华新能源材料有限公司 A kind of preparation method preparing lithium titanate cladding silicon-carbon composite cathode material
CN109319830A (en) * 2018-11-13 2019-02-12 北方奥钛纳米技术有限公司 Lithium titanate material and preparation method thereof, negative electrode tab, battery
CN109599553A (en) * 2018-11-20 2019-04-09 湘潭大学 A kind of hollow sphere nickel sodium manganate and preparation method thereof, sodium-ion battery positive plate and sodium-ion battery
CN109768234A (en) * 2018-12-24 2019-05-17 肇庆市华师大光电产业研究院 A kind of cobalt doped strontium titanates/graphene composite material, preparation method and application
CN109830677A (en) * 2018-12-29 2019-05-31 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, negative electrode tab, battery
CN109983610A (en) * 2016-11-18 2019-07-05 株式会社东芝 Non-aqueous electrolyte secondary battery
CN110112369A (en) * 2019-05-15 2019-08-09 桂林电子科技大学 Compound titanium deoxid film and the preparation method and application thereof
CN110176586A (en) * 2019-05-15 2019-08-27 桂林电子科技大学 Compound lithium titanate thin film and the preparation method and application thereof
CN110224118A (en) * 2019-05-15 2019-09-10 桂林电子科技大学 Compound manganese and oxygen compound film and the preparation method and application thereof
CN110289410A (en) * 2019-06-28 2019-09-27 陕西科技大学 A kind of MnO with height ratio capacity2The preparation method of/Ag composite material
CN110289414A (en) * 2019-07-04 2019-09-27 银隆新能源股份有限公司 A kind of lithium ion battery negative material and preparation method thereof
CN110603672A (en) * 2017-03-13 2019-12-20 通用汽车环球科技运作有限责任公司 Method for stabilizing Lithium Titanate Oxide (LTO) by surface coating
CN110923646A (en) * 2019-11-28 2020-03-27 桂林电子科技大学 Composite carbon film and preparation method and application thereof
CN112164803A (en) * 2020-11-03 2021-01-01 天目湖先进储能技术研究院有限公司 Three-dimensional dielectric polyacrylonitrile/nano silver-lithium composite material and preparation method thereof
CN112216827A (en) * 2020-09-21 2021-01-12 广东工业大学 Cu-doped modified LTO @ SnO2Composite material and preparation method and application thereof
CN114284483A (en) * 2021-12-24 2022-04-05 安徽博石高科新材料股份有限公司 Preparation and application of zirconium dioxide-coated lithium manganate cathode material
CN114744196A (en) * 2022-03-28 2022-07-12 蜂巢能源科技股份有限公司 C-doped and coated cobalt-free cathode material, preparation method and lithium ion battery
CN116960280A (en) * 2023-09-18 2023-10-27 宁德新能源科技有限公司 Negative electrode sheet, method of manufacturing the same, electrochemical device and electronic device including the same

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103326009B (en) * 2013-06-05 2015-08-19 深圳市斯诺实业发展有限公司 A kind of preparation method of high capacity lithium titanate anode material
CN103326010A (en) * 2013-06-05 2013-09-25 深圳市斯诺实业发展有限公司永丰县分公司 Process for preparing nano-silicon-doped composite-lithium-titanate anode materials
CN106486631B (en) * 2016-10-28 2023-08-22 珠海鹏辉能源有限公司 High-voltage quick-charge lithium ion battery and preparation method thereof
CN110299524B (en) * 2019-06-28 2022-04-01 陕西科技大学 MnO for preparing lithium ion battery negative electrode material2Method for producing Ag
CN114497469B (en) * 2020-11-11 2023-12-22 成都爱敏特新能源技术有限公司 Silicon monoxide-cobalt fluoride-graphene composite negative electrode material and preparation method thereof
CN115072703B (en) * 2022-08-02 2024-01-30 洛阳月星新能源科技有限公司 Composite anode material and preparation method and application thereof
CN115241461B (en) * 2022-09-20 2023-02-03 河北格力钛新能源有限公司 Method for preparing modified lithium titanate composite material and modified lithium titanate composite material
CN115548311A (en) * 2022-10-20 2022-12-30 福州大学 Fluorine doped TiO 2 (B) /rGO composite material and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1275342C (en) * 2004-12-17 2006-09-13 清华大学 Preparation method of spherical Li4Ti5O12 as lithium ion cell cathode material
CN100550482C (en) * 2005-03-30 2009-10-14 株式会社杰士汤浅 The lithium ion battery that is made of the lithium titanate that contains Mg is with active material and lithium ion battery
WO2006106700A1 (en) * 2005-03-30 2006-10-12 Gs Yuasa Corporation ACTIVE MATERIAL FOR LITHIUM ION BATTERY COMPOSED OF Al-CONTAINING LITHIUM TITANATE AND LITHIUM ION BATTERY
CN100530780C (en) * 2006-12-29 2009-08-19 深圳市贝特瑞电子材料有限公司 Composite lithium titanate electrode material and preparation method thereof
CN101373829B (en) * 2008-10-07 2011-05-11 深圳市贝特瑞新能源材料股份有限公司 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery

Cited By (112)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010040285A1 (en) * 2008-10-07 2010-04-15 深圳市贝特瑞新能源材料股份有限公司 Titanium-containing active material for negative electrodes and its production method and titanium-containing power lithium battery
CN101841017B (en) * 2009-03-16 2013-07-31 成都兴能新材料有限公司 Lithium titanate/carbon/carbon nano tube composite electrode material and preparation method thereof
CN101841017A (en) * 2009-03-16 2010-09-22 中国科学院成都有机化学有限公司 Lithium titanate/carbon/carbon nano tube composite electrode material and preparation method thereof
CN101540392B (en) * 2009-04-09 2011-04-06 西安建筑科技大学 Method for preparing lithium-manganese silicate of cathode material of lithium-ion battery
CN102414883A (en) * 2009-04-24 2012-04-11 夏普株式会社 Positive active material and nonaqueous secondary battery equipped with positive electrode including same
CN102414883B (en) * 2009-04-24 2014-04-02 夏普株式会社 Positive active material and nonaqueous secondary battery equipped with positive electrode including same
CN101877407B (en) * 2009-04-30 2013-06-19 比亚迪股份有限公司 Cathode active material, preparation method thereof and battery
TWI471270B (en) * 2009-05-26 2015-02-01 Ishihara Sangyo Kaisha Lithium titanate, method for preparing the same, and electrode active material and storage device using the same
US9452940B2 (en) 2009-05-26 2016-09-27 Ishihara Sangyo Kaisha, Ltd. Lithium titanate, electrode active material and electricity storage device each comprising the same
US9126847B2 (en) 2009-05-26 2015-09-08 Ishihara Sangyo Kaisha, Ltd. Lithium titanate, electrode active material and electricity storage device each comprising the same
CN101609883B (en) * 2009-07-13 2011-01-05 北京安华联合能源科技有限责任公司 Preparation method of nano-silver particle dispersed Li4Ti5O12 thin film lithium ion battery negative electrode
CN102013527B (en) * 2009-09-08 2012-08-29 清华大学深圳研究生院 Rechargeable zinc ion battery
CN102122708A (en) * 2010-01-08 2011-07-13 中国科学院物理研究所 Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole
US8765213B2 (en) 2010-02-06 2014-07-01 Tsinghua University Method for making lithium-ion battery electrode material
CN101800305A (en) * 2010-03-09 2010-08-11 福建师范大学 Method for depositing silicon film at surface of lithium titanate cathode of lithium ion battery
CN102201570A (en) * 2010-03-25 2011-09-28 清华大学 Preparation method for electrode material of lithium battery
US9425458B2 (en) 2010-03-25 2016-08-23 Tsinghua University Method for making lithium-ion battery electrode material
CN101800306A (en) * 2010-03-25 2010-08-11 陕西师范大学 Method for preparing tin oxide/carbon composite electrode material for lithium-ion batteries
TWI458164B (en) * 2010-03-30 2014-10-21 Hon Hai Prec Ind Co Ltd Method for making electrode material of lithium-ion battery
TWI403017B (en) * 2010-04-27 2013-07-21 Hon Hai Prec Ind Co Ltd Method for making electrode material of lithium-ion batteries
US9150424B2 (en) 2010-04-28 2015-10-06 Ishihara Sangyo Kaisha, Ltd. Lithium titanate, method for producing same, electrode active material containing the lithium titanate, and electricity storage device using the electrode active material
CN102869612A (en) * 2010-04-28 2013-01-09 石原产业株式会社 Novel lithium titanate, method for producing same, electrode active material containing the lithium titanate, and electricity storage device using the electrode active material
CN101859890A (en) * 2010-06-21 2010-10-13 惠州市赛能电池有限公司 Anode material of lithium ion battery
CN102442695A (en) * 2010-10-09 2012-05-09 合肥国轩高科动力能源有限公司 Preparation method of lithium titanate material of lithium ion battery
CN102013479A (en) * 2010-10-19 2011-04-13 合肥国轩高科动力能源有限公司 Method for preparing carbon-encapsulated zirconium-doped lithium titanium as lithium ion battery cathode material
CN102544438A (en) * 2010-12-20 2012-07-04 梅岭化工厂 Lithium titanate electrode doped with nanometer silver powder for lithium ion battery and preparation method for electrode
US8545735B2 (en) 2010-12-20 2013-10-01 Industrial Technology Research Institute Material of phosphorus-doped lithium titanium oxide with spinel structure and method of manufacturing the same
CN102024574A (en) * 2010-12-20 2011-04-20 浙江吉利汽车研究院有限公司 Method for preparing composite anode material of super capacitor lithium titanate
CN102544465A (en) * 2010-12-20 2012-07-04 财团法人工业技术研究院 Phosphorus-doped spinel-structured lithium titanium oxide material and preparation method thereof
CN102544465B (en) * 2010-12-20 2015-04-01 财团法人工业技术研究院 Phosphorus-doped spinel-structured lithium titanium oxide material and preparation method thereof
CN103384931A (en) * 2010-12-23 2013-11-06 野猫技术开发公司 Lithium-ion battery materials with improved properties
CN103503218B (en) * 2011-04-20 2016-02-03 松下知识产权经营株式会社 Rechargeable nonaqueous electrolytic battery
US10103382B2 (en) 2011-04-20 2018-10-16 Panasonic Intellectual Property Management Co., Ltd. Nonaqueous electrolyte secondary battery
CN103503218A (en) * 2011-04-20 2014-01-08 松下电器产业株式会社 Nonaqueous-electrolyte secondary battery
US20120270105A1 (en) * 2011-04-20 2012-10-25 Goto Natsumi Nonaqueous electrolyte secondary battery
US8920976B2 (en) * 2011-04-20 2014-12-30 Panasonic Corporation Nonaqueous electrolyte secondary battery
CN102867948B (en) * 2011-07-05 2016-05-11 三星Sdi株式会社 Compound, its method for making, negative active core-shell material, negative pole and lithium secondary battery
CN102867948A (en) * 2011-07-05 2013-01-09 三星Sdi株式会社 Composite, method of manufacturing the composite, anode active material including the composite, anode including the anode active material, and lithium secondary battery including the anode
CN102299297A (en) * 2011-07-30 2011-12-28 珠海锂源动力科技有限公司 Cathode of lithium ion battery and preparation method thereof
CN103178253A (en) * 2011-12-26 2013-06-26 太阳诱电株式会社 Lithium-titanium complex oxide, and battery electrode and lithium ion secondary battery containing same
CN102637873A (en) * 2012-03-27 2012-08-15 中宇锂电能源股份有限公司 Lithium ion battery cathode material and method for preparing same
CN102623698A (en) * 2012-04-16 2012-08-01 南京大学 Titanium lithium silicate, preparation method thereof and use of the same serving as electrode material of lithium battery
CN103390746B (en) * 2012-05-07 2016-08-03 电子科技大学 A kind of method improving lithium ionic cell cathode material lithium titanate performance
CN102683663A (en) * 2012-05-07 2012-09-19 宁德新能源科技有限公司 Lithium-ion secondary battery and anode material and manufacturing method thereof
CN102683663B (en) * 2012-05-07 2016-08-03 宁德新能源科技有限公司 Lithium rechargeable battery and negative material and preparation method thereof thereof
CN103390746A (en) * 2012-05-07 2013-11-13 电子科技大学 Method for improving performance of lithium ion battery cathode material lithium titanate
CN102683664A (en) * 2012-05-17 2012-09-19 湖南瑞翔新材料股份有限公司 Lithium titanate negative electrode material and preparation method thereof
CN102891304A (en) * 2012-09-24 2013-01-23 合肥国轩高科动力能源有限公司 Lithium titanate and lithium ion battery using lithium titanate as anode active substance
CN103779549B (en) * 2012-10-18 2015-11-18 上海纳米技术及应用国家工程研究中心有限公司 The preparation method of even particulate dispersion lithium ion battery electrode material nano lithium titanate
CN103779549A (en) * 2012-10-18 2014-05-07 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion batteryelectrode material nano lithium titanate with uniformly-dispersed particles
CN103840146A (en) * 2012-11-27 2014-06-04 西安物华新能源科技有限公司 Preparation method of high-tap-density lithium titanate material
CN103280567A (en) * 2013-03-06 2013-09-04 广州市东力电池实业有限公司 Li4Ti5O12 having surface chemically plated by metal, and preparation method thereof
CN103280567B (en) * 2013-03-06 2016-11-23 广东工业大学 A kind of surface chemical metal plating modifies Li4ti5o12and preparation method thereof
CN103259048A (en) * 2013-05-22 2013-08-21 南京双登科技发展研究院有限公司 Formation method for prolonging cycle life of lithium titanate battery
CN103337616A (en) * 2013-06-28 2013-10-02 上海电力学院 Metal oxide coated lithium titanate negative pole material and preparation method thereof
CN104347864A (en) * 2013-08-05 2015-02-11 神华集团有限责任公司 Material and preparation thereof, lithium ion battery electrode active substance containing material, electrode material, electrode and battery
WO2015067136A1 (en) * 2013-11-11 2015-05-14 江苏华东锂电技术研究院有限公司 Active material for negative electrode of lithium ion battery and preparation method therefor, and lithium ion battery
CN103872304A (en) * 2014-03-18 2014-06-18 中国科学院化学研究所 Novel magnesium secondary battery electrode material and application thereof
CN103872305A (en) * 2014-03-24 2014-06-18 四川兴能新材料有限公司 Preparation method of polyelectrolyte coated Li4Ti5O12 negative electrode material
CN103872305B (en) * 2014-03-24 2016-01-20 四川兴能新材料有限公司 The coated Li of polyelectrolyte 4ti 5o 12the preparation method of negative material
CN104979542A (en) * 2014-04-11 2015-10-14 上海杉杉科技有限公司 Modified lithium titanate composite material, preparation method and application thereof
CN104979542B (en) * 2014-04-11 2019-10-29 上海杉杉科技有限公司 A kind of modified lithium titanate composite material and preparation method and application
CN104009218A (en) * 2014-05-07 2014-08-27 上海应用技术学院 Preparation method of tin/lithium titanate composite electrode material as lithium ion battery negative electrode material
CN105185972A (en) * 2014-05-27 2015-12-23 中信国安盟固利动力科技有限公司 Composite titanate negative electrode material of lithium ion secondary battery and synthetic method thereof
CN105185972B (en) * 2014-05-27 2018-05-29 中信国安盟固利动力科技有限公司 The compound titanate negative material and its synthetic method of a kind of lithium rechargeable battery
CN104037400A (en) * 2014-07-09 2014-09-10 扬州大学 Preparation method of copper-doped lithium titanate lithium ion battery cathode material
CN104091917A (en) * 2014-07-10 2014-10-08 上海电力学院 Titanic oxide negative electrode material used as sodium-ion battery and preparation method of thereof
CN104577130A (en) * 2014-12-13 2015-04-29 山东神工海特电子科技有限公司 Flexible-packaged high-power lithium iron phosphate power battery
CN105990574A (en) * 2015-02-11 2016-10-05 微宏动力系统（湖州）有限公司 Coated lithium-rich negative electrode material and preparation method thereof
CN105990574B (en) * 2015-02-11 2020-01-14 微宏动力系统（湖州）有限公司 Coated lithium-rich negative electrode material and preparation method thereof
US10522869B2 (en) 2015-03-06 2019-12-31 Positec Power Tools (Suzhou) Co., Ltd. Battery, battery pack, and uninterruptible power supply
WO2016141861A1 (en) * 2015-03-06 2016-09-15 苏州宝时得电动工具有限公司 Battery, battery pack and uninterruptible power supply
US11211635B2 (en) 2015-03-06 2021-12-28 Positec Power Tools (Suzhou) Co., Ltd. Battery, battery pack, and uninterruptible power supply
WO2016165390A1 (en) * 2015-04-15 2016-10-20 田东 Preparation method for modified lithium titanate negative electrode material
WO2016192541A1 (en) * 2015-06-05 2016-12-08 田东 Method for manufacturing multiphase metal doped lithium titanate negative electrode material
WO2017024896A1 (en) * 2015-08-07 2017-02-16 田东 Preparation method for metal-doped composite lithium titanate negative electrode material
CN104966828A (en) * 2015-08-07 2015-10-07 田东 Preparation method of high-capacity lithium battery negative electrode material
CN105006555A (en) * 2015-08-07 2015-10-28 田东 Preparation method of compound lithium titanate anode material doped with metallic tin
CN105958021A (en) * 2016-05-27 2016-09-21 天津泰和九思科技有限公司 Lithium titanate composite material and preparation method thereof and lithium-ion battery
CN109983610B (en) * 2016-11-18 2022-09-23 株式会社东芝 Nonaqueous electrolyte secondary battery
CN109983610A (en) * 2016-11-18 2019-07-05 株式会社东芝 Non-aqueous electrolyte secondary battery
CN110603672B (en) * 2017-03-13 2022-10-14 通用汽车环球科技运作有限责任公司 Method for stabilizing Lithium Titanate Oxide (LTO) by surface coating
CN110603672A (en) * 2017-03-13 2019-12-20 通用汽车环球科技运作有限责任公司 Method for stabilizing Lithium Titanate Oxide (LTO) by surface coating
CN106935829A (en) * 2017-03-30 2017-07-07 上海动力储能电池系统工程技术有限公司 A kind of method for strengthening lithium ion battery lithium titanate material low-temperature characteristics
CN106935831A (en) * 2017-03-31 2017-07-07 深圳市国创新能源研究院 A kind of lithium titanate anode material for suppressing flatulence and its preparation method and application
CN107634221A (en) * 2017-08-18 2018-01-26 华北理工大学 A kind of synthetic method for the ferrous silicate lithium anode material that bismuth doping is prepared using iron tailings as raw material
CN107634221B (en) * 2017-08-18 2020-04-21 华北理工大学 Synthetic method for preparing bismuth-doped lithium ferrous silicate cathode material by taking iron tailings as raw materials
CN107732172A (en) * 2017-09-25 2018-02-23 中国计量大学 A kind of lithium ion battery negative material and preparation method thereof
CN107994219B (en) * 2017-11-27 2021-11-05 桑顿新能源科技(长沙)有限公司 Graphene-coated metal-doped composite cathode material and preparation method thereof
CN107994219A (en) * 2017-11-27 2018-05-04 桑顿新能源科技有限公司 A kind of metal-doped composite positive pole of graphene coated and preparation method thereof
CN108417785B (en) * 2018-01-11 2020-11-17 茆胜 Fluorine-nitrogen doped graphene coated lithium titanate composite material and preparation method thereof
CN108417785A (en) * 2018-01-11 2018-08-17 茆胜 Fluorine nitrogen-doped graphene coats lithium titanate composite material and preparation method thereof
CN108365194A (en) * 2018-02-06 2018-08-03 深圳市普锐能源科技有限公司 A kind of preparation method of composite negative electrode material of lithium ion battery
CN108695494A (en) * 2018-04-25 2018-10-23 福建翔丰华新能源材料有限公司 A kind of preparation method preparing lithium titanate cladding silicon-carbon composite cathode material
CN108682832A (en) * 2018-06-11 2018-10-19 四会市恒星智能科技有限公司 Lithium battery composite negative pole material and preparation method thereof
CN109319830A (en) * 2018-11-13 2019-02-12 北方奥钛纳米技术有限公司 Lithium titanate material and preparation method thereof, negative electrode tab, battery
CN109599553A (en) * 2018-11-20 2019-04-09 湘潭大学 A kind of hollow sphere nickel sodium manganate and preparation method thereof, sodium-ion battery positive plate and sodium-ion battery
CN109768234A (en) * 2018-12-24 2019-05-17 肇庆市华师大光电产业研究院 A kind of cobalt doped strontium titanates/graphene composite material, preparation method and application
CN109830677A (en) * 2018-12-29 2019-05-31 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, negative electrode tab, battery
CN110224118A (en) * 2019-05-15 2019-09-10 桂林电子科技大学 Compound manganese and oxygen compound film and the preparation method and application thereof
CN110176586A (en) * 2019-05-15 2019-08-27 桂林电子科技大学 Compound lithium titanate thin film and the preparation method and application thereof
CN110112369A (en) * 2019-05-15 2019-08-09 桂林电子科技大学 Compound titanium deoxid film and the preparation method and application thereof
CN110289410A (en) * 2019-06-28 2019-09-27 陕西科技大学 A kind of MnO with height ratio capacity2The preparation method of/Ag composite material
CN110289414A (en) * 2019-07-04 2019-09-27 银隆新能源股份有限公司 A kind of lithium ion battery negative material and preparation method thereof
CN110923646A (en) * 2019-11-28 2020-03-27 桂林电子科技大学 Composite carbon film and preparation method and application thereof
CN112216827A (en) * 2020-09-21 2021-01-12 广东工业大学 Cu-doped modified LTO @ SnO2Composite material and preparation method and application thereof
CN112164803A (en) * 2020-11-03 2021-01-01 天目湖先进储能技术研究院有限公司 Three-dimensional dielectric polyacrylonitrile/nano silver-lithium composite material and preparation method thereof
CN114284483A (en) * 2021-12-24 2022-04-05 安徽博石高科新材料股份有限公司 Preparation and application of zirconium dioxide-coated lithium manganate cathode material
CN114744196A (en) * 2022-03-28 2022-07-12 蜂巢能源科技股份有限公司 C-doped and coated cobalt-free cathode material, preparation method and lithium ion battery
CN114744196B (en) * 2022-03-28 2024-03-12 蜂巢能源科技股份有限公司 C-doped and coated cobalt-free positive electrode material, preparation method and lithium ion battery
CN116960280A (en) * 2023-09-18 2023-10-27 宁德新能源科技有限公司 Negative electrode sheet, method of manufacturing the same, electrochemical device and electronic device including the same
CN116960280B (en) * 2023-09-18 2024-04-30 宁德新能源科技有限公司 Negative electrode sheet, method of manufacturing the same, electrochemical device and electronic device including the same

Also Published As

Publication number Publication date
WO2010040285A1 (en) 2010-04-15
CN101373829B (en) 2011-05-11

Similar Documents

Publication Publication Date Title
CN101373829B (en) Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery
CN110690436B (en) Negative electrode material, preparation method thereof, prepared negative electrode plate and lithium ion battery
CN101635345B (en) Silicate anodal material for lithium ion battery and preparation method thereof
CN101540394B (en) Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material
CN101798079B (en) Cathode material of lithium-ion power battery and preparation method thereof
CN111384395B (en) Electrochemical device and electronic device
CN114665065B (en) Positive electrode plate and preparation method and application thereof
CN111342137B (en) Electrolyte and electrochemical device
CN102496714A (en) Anode active substance, production method thereof, and lithium ion battery employing anode active substance
CN1960040A (en) High-powered lithium ferric phosphate dynamic battery, and preparation technique
CN102290572A (en) Cathode active substance and cathode used for lithiumion secondary battery
WO2022133926A1 (en) Lithium-ion secondary battery and preparation method therefor, battery module, battery pack, and device
CN101540393B (en) Method for preparing lithium-manganese silicate of lithium-ion battery cathode material
US20230369591A1 (en) Negative-electrode active material and preparation method thereof, secondary battery, and battery module, battery pack, and apparatus containing such secondary battery
CN101774563A (en) High-voltage positive electrode material used by lithium ion battery and preparation method thereof
CN113644264A (en) Modification method of natural graphite negative electrode material
CN102104149A (en) Lithium iron phosphate composite anode material in lithium-ion battery and preparation method thereof
CN101894942B (en) LiFePO4/N combination electrode material and preparation method thereof
CN115411253A (en) Carbon-coated one-dimensional ferrous fluoride anode material and preparation method and application thereof
CN116742134A (en) Electrolyte and mixed lithium-sodium ion battery comprising same
Xu et al. Ultrafine LiNi 1/3 Co 1/3 Mn 1/3 O 2 powders via an enhanced thermal decomposition solid state reaction
JP2023503706A (en) Negative electrode sheet and manufacturing method thereof, secondary battery, battery module, battery pack and device
CN105990603A (en) High-power super-capacitor lithium battery and preparation method thereof
KR20220092566A (en) Negative electrode active material and manufacturing method thereof, secondary battery, and device comprising secondary battery
CN111342011A (en) Lithium iron phosphate/sulfur carbon composite cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery

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 BEITERUI NANO TECHNOLOGY CO., LTD.

Free format text: FORMER OWNER: SHENZHEN BTR NEW ENERGY MATERIAL CO., LTD.

Effective date: 20110630

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

Free format text: CORRECT: ADDRESS; FROM: 518055 BUILDING 8, LIANTANG INDUSTRY CITY, SHANGCUN VILLAGE, GONGMING TOWN, BAOAN DISTRICT, SHENZHEN CITY, GUANGDONG PROVINCE TO: 518106 BUILDING A3, 3RD INDUSTRIAL ZONE, XITIAN COMMUNITY, GONGMING OFFICE, GUANGMING NEW DISTRICT, SHENZHEN CITY, GUANGDONG PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20110630

Address after: 518106 A3 building, third industry zone, West Tian community, Gongming office, Guangming District, Guangdong, Shenzhen

Patentee after: Shenzhen Battery Nanotechnology Co., Ltd.

Address before: 518055, Baoan District Town, Gongming Town, Shenzhen City, Guangdong Province, Liantang, 8 industrial town

Patentee before: Shenzhen BTR New Energy Material Co., Ltd.

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20151123

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee after: Shenzhen BTR New Energy Material Co., Ltd.

Address before: 518106 A3 building, third industry zone, West Tian community, Gongming office, Guangming District, Guangdong, Shenzhen

Patentee before: Shenzhen Battery Nanotechnology Co., Ltd.

CP01 Change in the name or title of a patent holder

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee after: Beitrei New Materials Group Co., Ltd

Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee before: Shenzhen BTR New Energy Materials Inc.

CP01 Change in the name or title of a patent holder