CN101944609A - Zinc-doped lithium titanate material and preparation method thereof - Google Patents

Zinc-doped lithium titanate material and preparation method thereof Download PDF

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CN101944609A
CN101944609A CN2009101086051A CN200910108605A CN101944609A CN 101944609 A CN101944609 A CN 101944609A CN 2009101086051 A CN2009101086051 A CN 2009101086051A CN 200910108605 A CN200910108605 A CN 200910108605A CN 101944609 A CN101944609 A CN 101944609A
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lithium
lithium titanate
zinc
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李宝华
张标
杜鸿达
康飞宇
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Shenzhen Graduate School Tsinghua University
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    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a zinc-doped lithium titanate material and a preparation method thereof. The molecular formula of the lithium titanate material is Li(4-x)ZnxTi5O12, wherein x is more than 0 and less than 1. In the preparation method, lithium salt, a titanium compound and zinc oxide or zinc salt serve as raw materials and are calcined under inert atmosphere or reducing atmosphere. The lithium titanate material of the invention uses zinc to replace part of lithium in the lithium titanate; and the conductivity of the lithium titanate is improved by electronic compensation, and the large current capacity retention characteristic is obviously improved. The preparation method is convenient and simple, and the combined lithium titanate has good heavy current discharging performance and is suitable for industrial transformation.

Description

Lithium titanate material of zinc doping and preparation method thereof
Technical field
The present invention relates to a kind of electrode material and preparation method thereof, particularly a kind of spinel lithium titanate that is used for lithium ion battery and electrochemical capacitor and preparation method thereof.
Background technology
In recent years, lithium ion battery has obtained fast development, the lithium titanate of spinel structure comes into one's own day by day as a kind of lithium ion battery negative material with good circulation stability, high security, replace the life-span that traditional carbon negative pole material can improve battery greatly with it, fundamentally eliminate safe hidden trouble.Simultaneously, lithium titanate can also be used for the electrode material of electrochemical capacitor, and electrochemical capacitor is a kind of energy-storage travelling wave tube with high power density, will play an important role in fields such as electric automobiles.
The conductivity of pure phase lithium titanate is very low, and it is not good directly to be applied in the lithium ion battery performance, and therefore, the modification technology that is intended to improve conductivity is very important to improving material property.In known lithium titanate method of modifying, the method that generally adopts element doping and charcoal to coat improves its conductivity, improves heavy-current discharge performance.Introduced a kind of with Al element replacement lithium titanate part element method to lithium titanate modification, non-patent literature " Preparation and characteristic of carbon-coated Li for the CN101151747 denomination of invention for the Chinese invention patent application of " lithium ion battery that constitutes by the lithium titanate that contains Al with active material and lithium ion battery " as: publication number 4Ti 5O 12Anode material " (Journal of Power Source, 2007,174:1109-1112) introduced the method that coats raising lithium titanate heavy-current discharge performance by sucrose.The applicant finds under study for action, adopts zinc ion to mix and has positive effect for the high-rate discharge ability that improves lithium titanate, and the mechanism of action of this method is likely by electronic compensation, forms Ti 4+With Ti 3+Mixed valence, greatly improved the conductivity of lithium titanate.
Summary of the invention
The object of the present invention is to provide a kind of lithium titanate material that contains zinc and preparation method thereof,, improve its heavy-current discharge performance to improve the conductivity of lithium titanate.
The molecular formula of lithium titanate material of the present invention can be used Li 4-xZn xTi 5O 12Represent, wherein 0＜x＜1.Zn 2+Replace Li +, by electronic compensation, that is:
Figure B2009101086051D0000011
One of them electronics is corresponding to a Ti 4+Appraise at the current rate and be Ti 3+, improve the electronic conductivity of lithium titanate with this.
The preparation method of above-mentioned lithium titanate material may further comprise the steps:
A), mix
According to the mol ratio of Li, Zn, Ti in the molecular formula, calculate and take by weighing the lithium source, titanium source and the zinc source that need, they are mixed;
B), calcining
The mixture that step a) is made at inert atmosphere (as Ar, N 2Gas etc.) or reducing atmosphere (as Ar/H 2Gaseous mixture etc.) under,, promptly get lithium titanate material after the cooling with 750～900 ℃ of calcinings 10～24 hours.
Rapid a) in, can adopt ball milling method that lithium source, titanium source and zinc source are mixed.
In the step a), also lithium source, titanium source and the zinc source that takes by weighing can be added in the solvent together,, make gel by heating again by mixing.After adopting this method to mix, earlier with the gel that obtains at inert atmosphere (as Ar, N 2Gas etc.) or reducing atmosphere (as Ar/H 2Gaseous mixtures etc.) following 430～470 ℃ of heat treatments are 4～6 hours, and then calcine.
Can add the raw material of wood-charcoal material and coat in raw material further before calcining, to avoid grain growth, control grain morphology, the weight of the raw material of wood-charcoal material of adding is this raw material of wood-charcoal material and Li 4-xZn xTi 5 O 123～10% of total weight, wherein 0＜x＜1.The raw material of wood-charcoal material is preferentially selected carbon nano-fiber, acetylene black or sucrose for use.
The lithium source can be selected the inorganic salts of lithium or the organic salt of lithium for use.The titanium source is the compound of titanium.The zinc source can be selected the organic salt of zinc for use, as zinc acetate, zinc propionate, also can select the oxide of zinc for use, as zinc oxide, can also select the inorganic salts of zinc for use, as zinc sulfate.
The present invention also provides a kind of lithium ion battery, comprises the barrier film between positive electrode, negative electrode, electrolyte and the positive and negative electrode, it is characterized in that: it is Li that the active material of negative pole adopts molecular formula 4-xZn xTi 5O 12Lithium titanate material, 0＜x in the described molecular formula＜1.
The present invention also provides a kind of electrochemical capacitor, comprises the barrier film between positive electrode, negative electrode, electrolyte and the positive and negative electrode, it is characterized in that: it is Li that the active material of negative pole adopts molecular formula 4-xZn xTi 5O 12Lithium titanate material, 0＜x in the described molecular formula＜1.
Lithium titanate material of the present invention replaces part lithium in the lithium titanate with zinc and obtains, and by electronic compensation, has improved the conductivity of lithium titanate, and its high current capacity retention performance obviously improves, and has excellent cycle performance simultaneously.Through experiment test, the lithium ion battery made from the pure phase lithium titanate, when the specific capacity when 6C only is 0.5C 35%, and the lithium ion battery made from the lithium titanate of zinc doping amount x=0.25, when the specific capacity when 6C can reach 0.5C 65%, with the lithium ion battery that the lithium titanate of zinc doping amount x=0.5 is made, 80% the when specific capacity when 6C can reach 0.5C.
Lithium titanate material preparation method of the present invention is simple, convenient, and the lithium titanate heavy-current discharge performance that is synthesized is better, is fit to industry and transforms.
Description of drawings
Fig. 1 prepares X-ray diffraction (XRD) collection of illustrative plates of product for embodiment 1-4;
Fig. 2 is 2032 button half-cells of embodiment 5-7 preparation cycle performance figure when the heavy-current discharge;
Fig. 3 keeps performance map for 2032 button half-cells of the embodiment 5-7 preparation capacity when the heavy-current discharge;
Fig. 4 is that the capacity of 26650 cylindrical batteries when heavy-current discharge of embodiment 9 preparations keeps performance map.
Embodiment
Embodiment 1: preparation lithium titanate material Li 3ZnTi 5O 12
Select Li for use 2CO 3Make lithium source, TiO 2(rutile-type) makes titanium source, (CH 3COOH) 2Zn2H 2O does the zinc source, according to molecular formula Li 3ZnTi 5O 12Li is calculated and taken by weighing to the mol ratio of middle Li, Zn, Ti 3: 1: 5 2CO 3, TiO 2(rutile-type), (CH 3COOH) 2Zn2H 2O is for remedying the loss in lithium source under the high temperature, Li 2CO 3Excessive 5% (promptly at the Li that calculates according to made product molecular formula 2CO 3Add 5% on the weight basis).With acetone is solvent, and their speed ball milling 4h with 300rpm in planetary ball mill are mixed.After the oven dry, be warmed up to 800 ℃ with 5 ℃/min in atmosphere furnace, be incubated 12 hours, with the stove cooling, protective atmosphere is pure Ar gas, and protective atmosphere is used to avoid Ti 3+Oxidized, cooled sample grinding is sieved, obtain lithium titanate Li 3ZnTi 5O 12
Embodiment 2: preparation lithium titanate material Li 3.5Zn 0.5Ti 5O 12
Select Li for use 2CO 3Make lithium source, TiO 2(rutile-type) makes titanium source, (CH 3COOH) 2Zn2H 2O does the zinc source, according to molecular formula Li 3.5Zn 0.5Ti 5O 12Li is calculated and taken by weighing to the mol ratio of middle Li, Zn, Ti 3.5: 0.5: 5 2CO 3, TiO 2(rutile-type), (CH 3COOH) 2Zn2H 2O is for remedying the loss in lithium source under the high temperature, Li 2CO 3Excessive 5% (promptly at the Li that calculates according to made product molecular formula 2CO 3Add 5% on the weight basis).With acetone is solvent, and their speed ball milling 4h with 300rpm in planetary ball mill are mixed.After the oven dry, be warmed up to 800 ℃ with 5 ℃/min in atmosphere furnace, be incubated 12 hours, with the stove cooling, protective atmosphere is pure Ar gas, cooled sample is ground sieve, and obtains lithium titanate Li 3.5Zn 0.5Ti 5O 12
Embodiment 3: preparation lithium titanate material Li 3.75Zn 0.25Ti 5O 12
Select Li for use 2CO 3Make lithium source, TiO 2(rutile-type) makes titanium source, (CH 3COOH) 2Zn2H 2O does the zinc source, according to molecular formula Li 3.75Zn 0.25Ti 5O 12Li is calculated and taken by weighing to the mol ratio of middle Li, Zn, Ti 3.75: 0.25: 5 2CO 3, TiO 2(rutile-type), (CH 3COOH) 2Zn2H 2O is for remedying the loss in lithium source under the high temperature, Li 2CO 3Excessive 5% (promptly at the Li that calculates according to made product molecular formula 2CO 3Add 5% on the weight basis).With acetone is solvent, and their speed ball milling 4h with 300rpm in planetary ball mill are mixed.After the oven dry, be warmed up to 800 ℃ with 5 ℃/min in atmosphere furnace, be incubated 12 hours, with the stove cooling, protective atmosphere is pure Ar gas, cooled sample is ground sieve, and obtains lithium titanate Li 3.75Zn 0.25Ti 5O 12
Embodiment 4 (comparative example): preparation lithium titanate material Li 4Ti 5O 12
Select Li for use 2CO 3Make lithium source, TiO 2(rutile-type) does the titanium source, according to molecular formula Li 4Ti 5O 12Li is calculated and taken by weighing to the mol ratio of middle Li, Ti 4: 5 2CO 3, TiO 2(rutile-type) is for remedying the loss in lithium source under the high temperature, Li 2CO 3Excessive 5% (promptly at the Li that calculates according to made product molecular formula 2CO 3Add 5% on the weight basis).With acetone is solvent, and their speed ball milling 4h with 300rpm in planetary ball mill are mixed.After the oven dry, be warmed up to 800 ℃ with 5 ℃/min in atmosphere furnace, be incubated 12 hours, with the stove cooling, protective atmosphere is pure Ar gas, cooled sample is ground sieve, and obtains lithium titanate Li 4Ti 5O 12
The lithium titanate material Li of embodiment 1-4 preparation 3ZnTi 5O 12, Li 3.5Zn 0.5Ti 5O 12, Li 3.75Zn 0.25Ti 5O 12, Li 4Ti 5O 12X ray diffracting spectrum as shown in Figure 1, can see that x=1 (is Li up to the zinc doping amount 3ZnTi 5O 12) dephasign just appears in the sample, and this moment, capacity began to descend significantly.
Embodiment 5: the lithium titanate material Li that makes with embodiment 2 3.5Zn 0.5Ti 5O 12For active material prepares lithium ion battery.
With N-methyl pyrrolidone (NMP) is solvent, the lithium titanate material Li that embodiment 2 is made 3.5Zn 0.5Ti 5O 12Mix preparation slurry in back with conductive agent acetylene black and binding agent Kynoar (PVDF) at 8: 1: 1 by mass ratio, be coated on then on the Al paper tinsel, cold pressing after the oven dry and be washed into the sequin of 14mm diameter.With the sequin that makes is negative electrode, and metal lithium sheet is to electrode, and Celgard 2400 microporous polypropylene membranes are barrier film, the LiPF of 1M 6/ (EC+DEC) (1: 1, volume ratio) solution is that electrolyte is assembled into 2032 button half-cells.
Embodiment 6: the lithium titanate material Li that makes with embodiment 3 3.75Zn 0.25Ti 5O 12For active material prepares lithium ion battery.
With N-methyl pyrrolidone (NMP) is solvent, the lithium titanate material Li that embodiment 3 is made 3.75Zn 0.25Ti 5O 12Mix preparation slurry in back with conductive agent acetylene black and binding agent Kynoar (PVDF) at 8: 1: 1 by mass ratio, be coated on then on the Al paper tinsel, cold pressing after the oven dry and be washed into the sequin of 14mm diameter.With the sequin that makes is negative electrode, and metal lithium sheet is to electrode, and Celgard 2400 microporous polypropylene membranes are barrier film, the LiPF of lM 6/ (EC+DEC) (1: 1, volume ratio) solution is that electrolyte is assembled into 2032 button half-cells.
Embodiment 7 (comparative example): the lithium titanate material Li that makes with embodiment 4 4Ti 5O 12For active material prepares lithium ion battery.
With N-methyl pyrrolidone (NMP) is solvent, the lithium titanate material Li that embodiment 4 is made 4Ti 5O 12Mix preparation slurry in back with conductive agent acetylene black and binding agent Kynoar (PVDF) at 8: 1: 1 by mass ratio, be coated on then on the Al paper tinsel, cold pressing after the oven dry and be washed into the sequin of 14mm diameter.With the sequin that makes is negative electrode, and metal lithium sheet is to electrode, and Celgard 2400 microporous polypropylene membranes are barrier film, the LiPF of 1M 6/ (EC+DEC) (1: 1, volume ratio) solution is that electrolyte is assembled into 2032 button half-cells.
The performance of the battery that embodiment 5,6,7 makes compares:
Respectively to three kinds of battery discharges, test its specific capacity under 0.5C, 1C, 2C, 3C, 4C, 6C discharge-rate, every kind of battery carries out 10 tests under each multiplying power, test result as shown in Figure 2, the medium and small triangle representative of Fig. 2 is with Li 3.5Zn 0.5Ti 5O 12Be the battery (being the battery that embodiment 5 makes) of active material, hollow dots is represented with Li 3.75Zn 0.25Ti 5O 12Be the battery (being the battery that embodiment 6 makes) of active material, solid dot is represented with Li 4Ti 5O 12Battery (being the battery that embodiment 7 makes) for active material.As can be seen: with Li 4Ti 5O 12Influenced by discharging current very big for the battery specific capacity of active material, and when discharging current increased, the specific capacity decay was very fast.With Li 3.5Zn 0.5Ti 5O 12For the battery of active material with Li 3.75Zn 0.25Ti 5O 12For the battery of active material all has extraordinary cycle performance, and specific capacity influenced by discharging current less, especially with Li 3.5Zn 0.5Ti 5O 12For the battery of active material has goodish high current capacity conservation rate.In conjunction with Fig. 3, can be clear that the capacity of three kinds of batteries when heavy-current discharge keeps performance, can see the lithium ion battery made from the pure phase lithium titanate, when the specific capacity when 6C only is 0.5C 35%, and the lithium ion battery made from the lithium titanate of zinc doping amount x=0.25, when the specific capacity when 6C can reach 0.5C 65% is with the lithium ion battery that the lithium titanate of zinc doping amount x=0.5 is made, 80% the when specific capacity when 6C can reach 0.5C.As seen, by the doping zinc ion, improved the heavy-current discharge performance of lithium titanate material greatly.
Embodiment 8: prepare lithium titanate material Li with another kind of method 3.5Zn 0.5Ti 5O 12
Select LiCH for use 3COOH2H 2O makes lithium source, Ti (OCH (CH 3) 2) 4Make titanium source, (CH 3COOH) 2Zn2H 2O does the zinc source, according to molecular formula Li 3.5Zn 0.5Ti 5O 12LiCH is calculated and taken by weighing to the mol ratio of middle Li, Zn, Ti 3.5: 0.5: 5 3COOH2H 2O, Ti (OCH (CH 3) 2) 4(CH 3COOH) 2Zn2H 2O is for remedying the volatilization of calcining lithium under the high temperature, LiCH 3COOH2H 2O excessive 5% is (promptly at the LiCH that calculates according to made product molecular formula 3COOH2H 2Add 5% on the O weight basis), and take by weighing carbon nano-fiber (CNF) (CNF/ (Li of 5% (weight) 3.5Zn 0.5Ti 5O 12+ CNF)=5%), they are joined in the absolute ethyl alcohol together, mixed in 4 hours by magnetic agitation, heated 6 hours down at 60 ℃ then, obtain transparent colloidal sol, further heating makes the ethanol volatilization, obtains gel.With the 450 ℃ of heat treatment 5 hours under Ar gas atmosphere of the gel that obtains,, obtain the lithium titanate material Li of zinc doping then 800 ℃ of calcinings 12 hours down 3.5Zn 0.5Ti 5O 12
Embodiment 9: the lithium titanate material Li that makes with embodiment 8 3.5Zn 0.5Ti 5O 12For active material prepares lithium ion battery.
With N-methyl pyrrolidone (NMP) is solvent, the lithium titanate material Li that embodiment 8 is made 3.5Zn 0.5Ti 5O 12Mix preparation slurry in back with conductive agent acetylene black and binding agent Kynoar (PVDF) at 8: 1: 1 by mass ratio, be coated on then on the Al paper tinsel, cold pressing after the oven dry, obtain negative plate, then with LiFePO 4Be positive electrode, Celgard 2400 microporous polypropylene membranes are barrier film, the LiPF of 1M 6/ (EC+DEC) (1: 1, volume ratio) solution is electrolyte, is assembled into 26650 cylindrical batteries according to the capacity of 2Ah.The performance of test battery when 1C, 2C and 4C discharge, test result as shown in Figure 4, as can be seen, when discharge-rate increased, the battery capacity decay was slower, and circulated after 200 times, capacity is not decay almost, stability is better.

Claims (9)

1. lithium titanate material, it is characterized in that: its molecular formula is Li 4-xZn xTi 5O 12, 0＜x＜1 wherein.
2. the preparation method of the described lithium titanate material of claim 1 is characterized in that may further comprise the steps:
A), mix
According to the mol ratio of Li, Zn, Ti in the molecular formula, calculate and take by weighing the lithium source, titanium source and the zinc source that need, they are mixed;
B), calcining
The mixture that step a) is made with 750～900 ℃ of calcinings 10～24 hours, promptly gets lithium titanate material after the cooling under inert atmosphere or reducing atmosphere.
3. preparation method as claimed in claim 2 is characterized in that: adopt ball milling method to carry out the mixing in lithium source, titanium source and zinc source in the step a).
4. preparation method as claimed in claim 2 is characterized in that: in the step a) lithium source, titanium source and the zinc source that takes by weighing added in the solvent together, by mixing, make gel by heating again; Earlier with 430～470 ℃ of heat treatment 4～6 hours under inert atmosphere or reducing atmosphere of the gel that obtains, and then calcine in the step b).
5. as each described preparation method of claim 2-4, it is characterized in that: before calcining, add the raw material of wood-charcoal material and coat in raw material, the weight of the raw material of wood-charcoal material of adding is this raw material of wood-charcoal material and Li 4-xZn xTi 5O 123～10% of total weight, wherein 0＜x＜1.
6. preparation method as claimed in claim 5 is characterized in that: described raw material of wood-charcoal material is carbon nano-fiber, acetylene black or sucrose.
7. preparation method as claimed in claim 2 is characterized in that: described lithium source is the inorganic salts of lithium or the organic salt of lithium, and described titanium source is the compound of titanium, and described zinc source is the organic salt of zinc, the oxide of zinc or the inorganic salts of zinc.
8. a lithium ion battery comprises the barrier film between positive electrode, negative electrode, electrolyte and the positive and negative electrode, it is characterized in that: it is Li that the active material of negative pole adopts molecular formula 4-xZn xTi 5O 12Lithium titanate material, 0＜x in the described molecular formula＜1.
9. an electrochemical capacitor comprises the barrier film between positive electrode, negative electrode, electrolyte and the positive and negative electrode, it is characterized in that: it is Li that the active material of negative pole adopts molecular formula 4-xZn xTi 5O 12Lithium titanate material, 0＜x in the described molecular formula＜1.
CN2009101086051A 2009-07-07 2009-07-07 Zinc-doped lithium titanate material and preparation method thereof Pending CN101944609A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104916846A (en) * 2015-07-03 2015-09-16 中国第一汽车股份有限公司 Preparation method of nano-micron morphology Zn-doped lithium titanate for lithium-ion battery
CN105810901A (en) * 2016-03-14 2016-07-27 中国科学院广州能源研究所 Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material
CN106784681A (en) * 2016-12-20 2017-05-31 山东精工电子科技有限公司 A kind of preparation method of the lithium titanate composite material of granularity integrated distribution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221531B1 (en) * 1998-07-09 2001-04-24 The University Of Chicago Lithium-titanium-oxide anodes for lithium batteries
CN101035743A (en) * 2004-08-31 2007-09-12 原子能委员会 Titanium and dense lithium mixed oxide powder compound, method for producing said compound and compound-containing electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221531B1 (en) * 1998-07-09 2001-04-24 The University Of Chicago Lithium-titanium-oxide anodes for lithium batteries
CN101035743A (en) * 2004-08-31 2007-09-12 原子能委员会 Titanium and dense lithium mixed oxide powder compound, method for producing said compound and compound-containing electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104916846A (en) * 2015-07-03 2015-09-16 中国第一汽车股份有限公司 Preparation method of nano-micron morphology Zn-doped lithium titanate for lithium-ion battery
CN105810901A (en) * 2016-03-14 2016-07-27 中国科学院广州能源研究所 Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material
CN106784681A (en) * 2016-12-20 2017-05-31 山东精工电子科技有限公司 A kind of preparation method of the lithium titanate composite material of granularity integrated distribution
CN106784681B (en) * 2016-12-20 2019-07-05 山东精工电子科技有限公司 A kind of preparation method of the lithium titanate composite material of granularity integrated distribution

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Application publication date: 20110112