CN102054963A - Titanium acid lithium battery cathode material containing rare metal elements - Google Patents

Titanium acid lithium battery cathode material containing rare metal elements Download PDF

Info

Publication number
CN102054963A
CN102054963A CN2010102364697A CN201010236469A CN102054963A CN 102054963 A CN102054963 A CN 102054963A CN 2010102364697 A CN2010102364697 A CN 2010102364697A CN 201010236469 A CN201010236469 A CN 201010236469A CN 102054963 A CN102054963 A CN 102054963A
Authority
CN
China
Prior art keywords
lithium titanate
lithium
negative electrode
electrode material
cell negative
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.)
Pending
Application number
CN2010102364697A
Other languages
Chinese (zh)
Inventor
王雅和
王兴勤
王昕�
吴宁宁
葛焕增
蔡春华
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.)
RiseSun MGL New Energy Technology Co Ltd
Original Assignee
CITIC Guoan Mengguli Power Technology 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 CITIC Guoan Mengguli Power Technology Co Ltd filed Critical CITIC Guoan Mengguli Power Technology Co Ltd
Priority to CN2010102364697A priority Critical patent/CN102054963A/en
Publication of CN102054963A publication Critical patent/CN102054963A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention relates to titanium acid lithium battery cathode material containing rare metal elements, which comprises a synthesized lithium titanate material. A or a plurality of rare metal elements are contained in the lithium titanate material; the rare metal elements adopt Zr, Al, La, Ce, Pr, Nd, Sm and Dy or Ho; the contents of the rare metal elements are 0.01-3 wt percent by oxidate; the lithium and titanium molar ratio in the lithium titanate material is 0.7-1.2; and the titanium acid lithium battery cathode material is produced by adopting the processes of material mixing, ball milling and sieving, high-temperature treatment, secondary ball milling, high-temperature heat preservation and the like. The titanium acid lithium battery cathode material containing the rare metal elements is doped with the rare metal elements, improves the quick charging and discharging properties, improves the electrochemical capacity and has excellent cycle performance, good repeatability and high consistency; and furthermore, the titanium acid lithium battery cathode material has the advantages of low raw material cost, short synthesis time, low temperature, low requirements for equipment and simple manufacturing process and is suitable for industrial scale production.

Description

The lithium titanate cell negative electrode material that contains yttrium
Technical field
The present invention relates to the lithium battery critical material, particularly a kind of lithium titanate cell negative electrode material that contains yttrium.
Background technology
Along with development of science and technology, the various portable type electronic products of popularizing day by day, developing electric automobile etc. are all had higher requirement to all many-sides such as the energy density of battery power, useful lifes.In all batteries, characteristics such as lithium ion battery has voltage height, specific energy height, has extended cycle life, non-environmental-pollution are widely used.
But also there are some problems in lithium ion battery at present, and such as there being certain potential safety hazard, the electrode potential of carbon electrode and lithium metal is close, when battery overcharge, still may cause short circuit and form dendrite at carbon electrodes precipitating metal lithium.So " zero strain " material lithium-titanium composite oxide Li of 1.55v 4Ti 5O 12Become the focus of research gradually.Crystal structure can keep the stability of height in the process that this material embeds at lithium ion-deviates from, and has excellent cycle performance and discharge voltage stably.Because have higher electrode voltage, thereby avoided the generation of electrolyte decomposition phenomenon or diaphragm, security performance is good; And preparation Li 4Ti 5O 12Raw material sources abundanter.Therefore, Li 4Ti 5O 12A kind of more satisfactory reason ion battery negative material that can replace carbon of can yet be regarded as.
Because Li 4Ti 5O 12Conductivity of electrolyte materials, though can improve its fast charging and discharging performance and high rate during charging-discharging by mixing, electrochemical capacity is relatively poor.
Summary of the invention
For overcoming above-mentioned defective, improve Li 4Ti 5O 12Performance, the invention provides a kind of lithium titanate cell negative electrode material that contains yttrium.
The lithium titanate cell negative electrode material that the present invention contains yttrium comprises, comprises synthetic lithium titanate material, wherein: contain one or more yttriums in the described lithium titanate material.
Described yttrium is Zr, Al, La, Ce, Pr, Nd, Sm, Dy or Ho.
Described yttrium content is by oxide, and content is 0.01-3wt%.
Lithium titanium mol ratio is 0.7-1.2 in the described lithium titanate material.
The preparation method of the described lithium titanate cell negative electrode material that contains yttrium is as follows:
6) additive with lithium salts, titanium dioxide and yttrium carries out batch mixing with ball milling method, adds the dispersant ball milling 0.5-10 hour, up to mixing, then the uniform slurry of solids of ball milling is removed dispersant with microwave drying, obtains presoma;
7) presoma is put into the Muffle furnace heat treated, heating-up temperature 300-700 ℃, 0.5-5 hour heating time;
8) after the heating product naturally cooled to room temperature, pulverization process was crossed 150 mesh sieves;
9) crushed material divides three sections insulations to handle, and is warming up to 300-550 ℃ earlier, is incubated 0.5-3 hour; Then heat up 700-1100 ℃, temperature retention time 1-10 hour, be cooled to 300-600 ℃ at last, continue insulation 0.5-3 hour, get synthetic material;
10) above-mentioned synthetic material after sieving, 150 mesh sieves is obtained final products spinelle Li 4Ti 5O 12
Wherein: described lithium salts is one or more mixtures in lithium carbonate, lithium hydroxide, lithium nitrate and the lithium acetate;
It is one or both mixtures in anatase titanium dioxide or the rutile-type that described titanium dioxide is selected structure for use;
The described additive that contains yttrium is the oxide of zirconium, aluminium, lanthanum, cerium, praseodymium, neodymium, samarium, dysprosium or holmium or in the hydroxide one or more;
Described organic solvent is one or more mixtures in methyl alcohol, absolute ethyl alcohol, acetone or the citric acid.
The present invention contains the lithium titanate cell negative electrode material of yttrium, and the doping yttrium has improved fast charging and discharging performance, has improved electrochemistry capacitance, cycle performance excellence, favorable reproducibility, consistency height; And raw material is cheap, generated time is short, temperature low low for equipment requirements, preparation technology is simple, is fit to industrial-scale production.
Description of drawings
Fig. 1 is the SEM figure of the present invention's lithium titanate cell negative electrode material (embodiment four) of containing yttrium;
Fig. 2 is the present invention's lithium titanate cell negative electrode material (embodiment four) of containing yttrium and the XRD comparison diagram of standard diagram;
Fig. 3 is the cyclic curve figure of the present invention's lithium titanate cell negative electrode material (embodiment four) of containing yttrium;
Fig. 4 is the first charge-discharge voltage curve of the present invention's lithium titanate cell negative electrode material (embodiment four) of containing yttrium.
Embodiment
Below in conjunction with embodiment lithium titanate industrial preparative method of the present invention is done more detailed explanation.
Embodiment one:
Selecting bicarbonate lithia, anatase titanium dioxide and cerium oxide for use is raw material, and wherein: the mol ratio of lithium hydroxide and anatase titanium dioxide is 0.81: 1, and cerium oxide accounts for the 1wt% of three kinds of raw material gross weights.Three kinds of raw materials are mixed, add the methyl alcohol dispersant, ball milling is 6 hours on ball mill, gets presoma after the microwave drying.
Presoma is for further processing as follows: elder generation is under 500 ℃ of temperature under air atmosphere, high-temperature process 2 hours, cooling back ball milling is crossed 150 mesh sieves, the afterproduct that sieves is incubated 2 hours again under 500 ℃ of temperature, be warmed up to 800 ℃ of insulations 8 hours then, cool to 600 ℃ of insulations 2 hours again, be cooled to room temperature cooling back ball milling at last and cross 150 mesh sieves and get lithium titanate Li 4Ti 5O 12Sample.Observe through electron microscope (SEM), material particles is even, tiny, and for single spinel structure pH value is 10.8, grain size analysis particle D50 is 5um after X-ray powder diffraction (XRD) test.
With synthetic Li 4Ti 5O 12, acetylene black and electrically conductive graphite mixture, bonding agent polyvinylidene fluoride (PVDF) mix by mass ratio at 90: 4: 6, is coated on the aluminium foil, is cut into pole piece after the drying.With electrolyte LiPF 6It is to form electrolyte in 1: 1 the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) that salt is dissolved in volume ratio, the concentration of electrolyte is 1mol/L, with lithium metal is to electrode, is assembled into button cell in the argon gas case, carries out electrochemical property test.Discharging and recharging is 0.2C first, and secondary is later on 1.0C, and voltage range is 0.8-2.5V, and specific capacity is 163mAh/g first, and decaying appears in single repeatedly circulation back capacity, and 100 times circulation back capability retention is 96%.
Embodiment two:
Selecting lithium carbonate, anatase titanium dioxide and neodymia for use is raw material, and wherein: the mol ratio of lithium carbonate and anatase titanium dioxide is 0.85: 1, and neodymia accounts for the 3wt% of three kinds of raw material gross weights.Three kinds of raw materials are mixed, add alcohol dispersant, ball milling is 7 hours on ball mill, gets presoma after the microwave drying.
Presoma is for further processing following be for further processing with embodiment one.Observe through electron microscope (SEM), material particles is even, tiny, and for single spinel structure pH value is 10.5, grain size analysis particle D50 is 4um after X-ray powder diffraction (XRD) test.
The preparation of pole piece, the assembling of button cell and electrochemical property test are with embodiment one.Specific capacity is 160mAh/g first, the superior performance of material.
Embodiment three:
Selecting lithium hydroxide, golden red type titanium dioxide and cerium oxide for use is raw material, and wherein: the mol ratio of lithium hydroxide and anatase titanium dioxide is 0.8: 1, and cerium oxide accounts for the 0.5wt% of three kinds of raw material gross weights.Three kinds of raw materials are mixed, add alcohol dispersant, ball milling is 6 hours on ball mill, gets presoma after the microwave drying.
Presoma is for further processing following be for further processing with embodiment one.Observe through electron microscope (SEM), material particles is even, tiny, and for single spinel structure pH value is 10.9, grain size analysis particle D50 is 5um after X-ray powder diffraction (XRD) test.
The preparation of pole piece, the assembling of button cell and electrochemical property test are with embodiment one.Specific capacity is 150mAh/g first, the superior performance of material.
Embodiment four:
Selecting lithium carbonate lithium hydroxide, anatase titanium dioxide for use is raw material, and wherein: the mol ratio of lithium hydroxide and anatase titanium dioxide is 0.9: 1, and zirconia accounts for the 2wt% of three kinds of raw material gross weights.Three kinds of raw materials are mixed, add alcohol dispersant, ball milling is 8 hours on ball mill, gets presoma after the microwave drying.
Presoma is for further processing following be for further processing with embodiment one.Observe through electron microscope (SEM), material particles is even, tiny, is single spinel structure after X-ray powder diffraction (XRD) test, and pH value is 10.9, and grain size analysis particle D50 is 2um.
The preparation of pole piece, the assembling of button cell and electrochemical property test are with embodiment one.0.5C specific capacity is 173mAh/g, 1C specific capacity 164mAh/g, and cycle performance is superior, and capability retention is 100% after 200 circulations.

Claims (9)

1. a lithium titanate cell negative electrode material that contains yttrium comprises synthetic lithium titanate material, it is characterized in that: contain one or more yttriums in the described lithium titanate material.
2. the lithium titanate cell negative electrode material that contains yttrium according to claim 1 is characterized in that: described rare element is Zr, Al, La, Ce, Pr, Nd, Sm, Dy or Ho.
3. the lithium titanate cell negative electrode material that contains yttrium according to claim 2 is characterized in that: described yttrium content is by oxide, and content is 0.01-3wt%.
4. the lithium titanate cell negative electrode material that contains yttrium according to claim 3 is characterized in that: lithium titanium mol ratio is 0.7-1.2 in the described lithium titanate material.
5. the lithium titanate cell negative electrode material that contains yttrium according to claim 4 is characterized in that: the preparation method of the described lithium titanate cell negative electrode material that contains yttrium is as follows:
1) lithium salts, titanium dioxide and the additive that contains yttrium are carried out batch mixing with ball milling method, added the dispersant ball milling 0.5-10 hour,, then the uniform slurry of solids of ball milling is removed dispersant with microwave drying, obtain presoma up to mixing;
2) presoma is put into the Muffle furnace heat treated, heating-up temperature 300-700 ℃, 0.5-5 hour heating time;
3) after the heating product naturally cooled to room temperature, pulverization process was crossed 150 mesh sieves;
4) crushed material divides three sections insulations to handle, and is warming up to 300-550 ℃ earlier, is incubated 0.5-3 hour; Then heat up 700-1100 ℃, temperature retention time 1-20 hour, be cooled to 300-600 ℃ at last, continue insulation 0.5-3 hour, get synthetic material;
5) above-mentioned synthetic material after sieving, 150 mesh sieves is obtained final products spinelle Li 4Ti 5O 12
6. the lithium titanate cell negative electrode material that contains yttrium according to claim 5 is characterized in that: described lithium salts is one or more mixtures in lithium carbonate, lithium hydroxide, lithium nitrate and the lithium acetate.
7. the lithium titanate cell negative electrode material that contains yttrium according to claim 6 is characterized in that: it is one or both mixtures in anatase titanium dioxide or the rutile-type that described titanium dioxide is selected structure for use.
8. the lithium titanate cell negative electrode material that contains yttrium according to claim 7 is characterized in that: the described additive that contains yttrium is the oxide of zirconium, aluminium, lanthanum, cerium, praseodymium, neodymium, samarium, dysprosium or holmium or in the hydroxide one or more.
9. the lithium titanate cell negative electrode material that contains yttrium according to claim 8 is characterized in that: described organic solvent is one or more mixtures in methyl alcohol, absolute ethyl alcohol, acetone or the citric acid.
CN2010102364697A 2010-07-22 2010-07-22 Titanium acid lithium battery cathode material containing rare metal elements Pending CN102054963A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010102364697A CN102054963A (en) 2010-07-22 2010-07-22 Titanium acid lithium battery cathode material containing rare metal elements

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010102364697A CN102054963A (en) 2010-07-22 2010-07-22 Titanium acid lithium battery cathode material containing rare metal elements

Publications (1)

Publication Number Publication Date
CN102054963A true CN102054963A (en) 2011-05-11

Family

ID=43959088

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010102364697A Pending CN102054963A (en) 2010-07-22 2010-07-22 Titanium acid lithium battery cathode material containing rare metal elements

Country Status (1)

Country Link
CN (1) CN102054963A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102637864A (en) * 2012-05-10 2012-08-15 山东大学 Lanthanum-doped lithium titanate cathode material and preparation method thereof
CN103022461A (en) * 2012-12-13 2013-04-03 上海纳米技术及应用国家工程研究中心有限公司 Rare-earth metal doped micro-nanometer lithium titanate cathode material and preparation method thereof
CN103107323A (en) * 2012-12-27 2013-05-15 东莞上海大学纳米技术研究院 Cerium-doped modified lithium titanate negative material of lithium ion secondary battery and preparation method thereof
CN103346310A (en) * 2013-07-11 2013-10-09 苏州懿源宏达知识产权代理有限公司 Preparation method of carbon-clad holmium-doped lithium titanate composite negative material
CN104466152A (en) * 2014-12-02 2015-03-25 赵县强能电源有限公司 Preparation method of lithium ion battery cathode material (lithium titanate)
CN104638255A (en) * 2015-02-02 2015-05-20 斌源材料科技（上海）有限公司 Lithium titanate/carbon composite material and method for preparing material
CN105531231A (en) * 2013-05-23 2016-04-27 Posco公司 Manufacturing method of lithium-titanium composite oxide in which different metals are doped, and lithium-titanium composite oxide manufactured thereby in which different metals are doped
CN106159223A (en) * 2016-07-01 2016-11-23 天津普兰能源科技有限公司 A kind of preparation method of lithium titanate material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456581A (en) * 2009-01-05 2009-06-17 中信国安盟固利新能源科技有限公司 Method for preparing lithium ion secondary battery cathode material lithium titanate containing rare-earth element
CN101567442A (en) * 2008-07-28 2009-10-28 新乡市中科科技有限公司 Method for preparing spinel lithium titanate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101567442A (en) * 2008-07-28 2009-10-28 新乡市中科科技有限公司 Method for preparing spinel lithium titanate
CN101456581A (en) * 2009-01-05 2009-06-17 中信国安盟固利新能源科技有限公司 Method for preparing lithium ion secondary battery cathode material lithium titanate containing rare-earth element

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
唐致远等: "Mg2+、Zr4+离子掺杂对Li4Ti5O12 电化学性能的影响", 《精细化工》 *
黄莎华等: "Li3.608Al0.085Ti5O11.932的制备和电化学性能研究", 《第十二届中国固态离子学学术会议论文集》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102637864A (en) * 2012-05-10 2012-08-15 山东大学 Lanthanum-doped lithium titanate cathode material and preparation method thereof
CN103022461A (en) * 2012-12-13 2013-04-03 上海纳米技术及应用国家工程研究中心有限公司 Rare-earth metal doped micro-nanometer lithium titanate cathode material and preparation method thereof
CN103107323A (en) * 2012-12-27 2013-05-15 东莞上海大学纳米技术研究院 Cerium-doped modified lithium titanate negative material of lithium ion secondary battery and preparation method thereof
CN105531231A (en) * 2013-05-23 2016-04-27 Posco公司 Manufacturing method of lithium-titanium composite oxide in which different metals are doped, and lithium-titanium composite oxide manufactured thereby in which different metals are doped
CN103346310A (en) * 2013-07-11 2013-10-09 苏州懿源宏达知识产权代理有限公司 Preparation method of carbon-clad holmium-doped lithium titanate composite negative material
CN104466152A (en) * 2014-12-02 2015-03-25 赵县强能电源有限公司 Preparation method of lithium ion battery cathode material (lithium titanate)
CN104466152B (en) * 2014-12-02 2018-02-23 赵县强能电源有限公司 A kind of preparation method of lithium ionic cell cathode material lithium titanate
CN104638255A (en) * 2015-02-02 2015-05-20 斌源材料科技（上海）有限公司 Lithium titanate/carbon composite material and method for preparing material
CN104638255B (en) * 2015-02-02 2017-11-24 斌源材料科技（上海）有限公司 A kind of metatitanic acid lithium/carbon composite material and preparation method thereof
CN106159223A (en) * 2016-07-01 2016-11-23 天津普兰能源科技有限公司 A kind of preparation method of lithium titanate material

Similar Documents

Publication Publication Date Title
JP5756625B2 (en) Method for producing positive electrode active material for lithium battery
US9437873B2 (en) Spinel-type lithium manganese-based composite oxide
CN102054963A (en) Titanium acid lithium battery cathode material containing rare metal elements
KR20150073969A (en) Li-Ni COMPOSITE OXIDE PARTICLE POWDER AND METHOD FOR MANUFACTURING SAME, AND NONAQUEOUS ELECTROLYTE SECONDARY CELL
Hou et al. Drastic enhancement in the rate and cyclic behavior of LiMn2O4 electrodes at elevated temperatures by phosphorus doping
CN109873140B (en) Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material
CN102328952B (en) Preparation method for spherical lithium titanate material
CN101777644A (en) Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate
KR20150073970A (en) Li-Ni COMPLEX OXIDE PARTICLE POWDER AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY
CN115023831A (en) Mixed powder for all-solid-state lithium-ion battery, mixed paste for all-solid-state lithium-ion battery, electrode, and all-solid-state lithium-ion battery
CN101800307A (en) Method for preparing carbon-coated manganese-doped lithium titanate negative electrode material of lithium ion battery
CN103682292B (en) The lithium titanate material preparation method of high-tap density
CN105789607A (en) Preparation method of lithium titanate anode material doped with rare earth
CN101986445A (en) Method for producing lithium battery cathode material lithium titanate
CN103151506A (en) Preparation method of nanoscale zirconium-doped lithium titanate material
CN102683668A (en) Spinel nickel manganese-based oxide cathode material and preparation process thereof
CN101764212A (en) Method for preparing spinelle lithium titanate for lithium ion battery negative electrode material
KR20160009015A (en) Positive electrode active material for lithium secondary battery
CN1183615C (en) Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator
JP2004311427A (en) Positive electrode active material for lithium secondary battery and its manufacturing method and non-aqueous lithium secondary battery
CN101456581A (en) Method for preparing lithium ion secondary battery cathode material lithium titanate containing rare-earth element
Guo et al. Synthesis of high-purity LiMn 2 O 4 with enhanced electrical properties from electrolytic manganese dioxide treated by sulfuric acid-assisted hydrothermal method
CN103219509B (en) Preparation method of lithium manganese oxide spinel positive material
CN102623704A (en) Preparation method of lithium titanate-carbon fiber composite material for cathode of lithium ion battery
CN107324379A (en) A kind of high power capacity lithium titanate material preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20110511