CN103107323A - Cerium-doped modified lithium titanate negative material of lithium ion secondary battery and preparation method thereof - Google Patents

Cerium-doped modified lithium titanate negative material of lithium ion secondary battery and preparation method thereof Download PDF

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CN103107323A
CN103107323A CN2012105792991A CN201210579299A CN103107323A CN 103107323 A CN103107323 A CN 103107323A CN 2012105792991 A CN2012105792991 A CN 2012105792991A CN 201210579299 A CN201210579299 A CN 201210579299A CN 103107323 A CN103107323 A CN 103107323A
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cerium
lithium
source
titanate
lithium titanate
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刘洪江
程崇领
施利毅
薛鑫
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DONGGUAN-SHU INSTITUTE OF NANOTECHNOLOGY
University of Shanghai for Science and Technology
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DONGGUAN-SHU INSTITUTE OF NANOTECHNOLOGY
University of Shanghai for Science and Technology
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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

Abstract

The invention discloses a cerium-doped modified lithium titanate negative material of a lithium ion secondary battery. The cerium-doped modified lithium titanate negative material is characterized in that the negative material is prepared from a lithium source, a lithium source and a cerium source; cerium is uniformly distributed in the nano lithium titanate by in-situ synthesis; and the composite negative material contains 0.01% to 1% of cerium by weight, and 99% to 99.0% of lithium titanate by weight. The invention also discloses a preparation method of the cerium-doped modified lithium titanate negative material of the lithium ion secondary battery. The lithium titanate material and the preparation method thereof provided by the invention can improve the high-rate charge/discharge performance and the conductivity of the negative material by adding cerium in the lithium titanate material, thereby meeting the requirement on lithium ion batteries in modern society.

Description

Lithium ion secondary battery cathode material lithium titanate of a kind of cerium doping vario-property and preparation method thereof
Technical field
The invention belongs to the electrochemical power source technical field of material, be specifically related to a kind of lithium ion secondary battery cathode material lithium titanate and hydrothermal preparing process thereof of cerium doping vario-property.
Background technology
Along with the development of science and technology, various portable type electronic products are day by day universal, and developing electric automobile etc. are had higher requirement to all many-sides such as the energy density of battery power, useful lifes.In all batteries, the characteristics such as lithium ion battery has that voltage is high, specific energy is high, has extended cycle life, non-environmental-pollution, to be widely used in the portable electric appts such as mobile phone, notebook computer, also will be used widely in fields such as electric automobile, satellite and space flight.
But at present also there are some problems in lithium ion battery, for example has certain potential safety hazard, and the electrode potential of carbon electrode and lithium metal is close, when battery overcharge, still may form dendrite at carbon electrodes precipitating metal lithium and cause short circuit.So the current potential with respect to lithium electrode is " zero strain " material lithium-titanium composite oxide Li of 1.55v 4Ti 5O 12Become gradually the focus of research.This material crystal structure in the process that lithium ion embeds-deviates from can keep the stability of height to make it have good cycle performance and discharge voltage stably.Thereby due to the generation that has higher electrode voltage and avoided electrolyte decomposition phenomenon or diaphragm, security performance is good, and preparation Li 4Ti 5O 12Raw material sources abundanter, so Li 4Ti 5O 12It is a kind of desirable lithium ion battery negative material that is used for energy storage.
But the intrinsic conductivity of lithium titanate is 10-9S/cm, belongs to typical insulator, poorly conductive, and heavy-current discharge performance is poor.Usually the preparation method plays a crucial role to the final performance of material, now preparation spinel type lithium titanate (Li commonly used 4Ti 5O 12) method high temperature solid phase synthesis, sol-gal process are arranged.The lithium titanate material high rate charge-discharge poor-performing of these two kinds of method preparations, in course of reaction, energy consumption is large.In view of this, be necessary to provide a kind of energy consumption less, have the preparation method of the lithium titanate material of satisfactory electrical conductivity and large high rate performance.
Summary of the invention
The objective of the invention is for above-mentioned deficiency, lithium ion secondary battery cathode material lithium titanate of a kind of cerium doping vario-property and preparation method thereof is provided, by add cerium in lithium titanate material, thereby improve the high rate charge-discharge performance of negative material, improve the conductivity of material, to satisfy modern society to the requirement of lithium ion battery applications.
The technical scheme that the present invention adopts for achieving the above object is:
A kind of lithium ion secondary battery cathode material lithium titanate of cerium doping vario-property, it is made by following component: titanium source, lithium source and cerium source; Realize the even distribution of cerium in nano lithium titanate by original position is compound, wherein cerium shared part by weight in composite negative pole material is 0.01～1%, and lithium titanate shared part by weight in composite negative pole material is 99～99.99%.
Described titanium source is titanium sulfate, butyl titanate, isopropyl titanate, metatitanic acid, amorphous titania, business anatase titanium dioxide, one or more in rutile titanium dioxide.
Described lithium source is one or more in lithia, lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium chloride, lithium nitrate.
Described cerium source is one or more in cerium oxide, cerous carbonate, cerium hydroxide, cerous acetate, cerium oxalate, cerium chloride, cerous nitrate, comprise cerium bromide.
A kind of preparation method of the lithium ion secondary battery cathode material lithium titanate according to above-mentioned cerium doping vario-property, it comprises the following steps:
(1) measure the titanium source, add in deionized water, make dispersion liquid A;
(2) measuring ratio with the described titanium of step (1) source amount of substance is 1: 1.0～1.2 lithium source, is scattered in deionized water;
(3) measure the cerium source, the quality that makes contained cerium is 0.01～1% of titanium source and lithium source gross mass, and the cerium source is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, then the baking oven that is placed in 120～200 ℃ of conditions reacted 5～48 hours, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with deionized water or ethanol washing, drying obtains Li under 60～120 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 1～5 hour under nitrogen atmosphere, 400～1000 ℃ of conditions, products therefrom namely gets nanoscale Li 4Ti 5O 12/ Ce material.
The invention has the beneficial effects as follows:
1, the present invention adopts is that hydrothermal synthesis method is processed with solid phase and combined, and the titanium source is hydrolyzed in solvent with the lithium source again and reacts under higher temperatures, has realized other dispersion of molecular level, and being more evenly distributed of particle makes the size of product can remain on nano-grade size.Nano level lithium titanate material is realized ion-exchange simultaneously under the hydro-thermal dynamic environment, react more abundant, heat energy and kinetic energy are converted to the material internal energy, greatly shortened the processing time, improve productive rate, reduced energy resource consumption and cost, simplified process conditions, the raw material range of choice is wide, is easy in industrial enforcement.
2, the present invention's doped Ce under hydrothermal condition, shortened heat treatment time, the material grains refinement, and even structure is conducive to the migration of lithium ion and moves out.
3, doped Ce of the present invention has improved lithium titanate anode electrode material specific capacity.
Description of drawings
Fig. 1 is the X-ray diffractogram of the prepared material of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph that the present invention prepares material;
Fig. 3 is embodiment 2 and the cycle performance curve of the prepared material of Comparative Examples under the 0.1C multiplying power;
Fig. 4 is the first charge-discharge curve of the prepared material of embodiment 2 under the 0.1C multiplying power.
Embodiment
Embodiment 1: referring to Fig. 1 to Fig. 2, and the lithium ion secondary battery cathode material lithium titanate of the cerium doping vario-property that the present embodiment provides, it is made by following component: titanium source, lithium source and cerium source; Realize the even distribution of cerium in nano lithium titanate by original position is compound, wherein cerium shared part by weight in composite negative pole material is 0.01～1%, and lithium titanate shared part by weight in composite negative pole material is 99～99.99%.
Described titanium source is titanium sulfate, butyl titanate, isopropyl titanate, metatitanic acid, amorphous titania, business anatase titanium dioxide, one or more in rutile titanium dioxide.
Described lithium source is one or more in lithia, lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium chloride, lithium nitrate.
Described cerium source is one or more in cerium oxide, cerous carbonate, cerium hydroxide, cerous acetate, cerium oxalate, cerium chloride, cerous nitrate, comprise cerium bromide.
A kind of preparation method of the lithium ion secondary battery cathode material lithium titanate according to above-mentioned cerium doping vario-property, it comprises the following steps:
(1) measure the titanium source, add in deionized water, make dispersion liquid A;
(2) measuring ratio with the described titanium of step (1) source amount of substance is 1: 1.0～1.2 lithium source, is scattered in deionized water;
(3) measure the cerium source, the quality that makes contained cerium is 0.01～1% of titanium source and lithium source gross mass, and the cerium source is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, then the baking oven that is placed in 120～200 ℃ of conditions reacted 5～48 hours, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with deionized water or ethanol washing, drying obtains Li under 60～120 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 1～5 hour under nitrogen atmosphere, 400～1000 ℃ of conditions, products therefrom namely gets nanoscale Li 4Ti 5O 12/ Ce material.
Embodiment 2: referring to Fig. 1 to Fig. 4, the present embodiment provides lithium ion secondary battery cathode material lithium titanate of a kind of cerium doping vario-property and preparation method thereof, and its method is substantially the same manner as Example 1, and its difference is, it comprises the following steps:
(1) measure the 28.4ml isopropyl titanate, splash in the 50ml deionized water, make dispersion liquid A;
(2) measure 4.2g hydronium(ion) oxidation lithium, with the ratio of the described isopropyl titanate amount of substance of step (1) be 1: 1.0, be scattered in the 50ml deionized water;
(3) measure the cerous nitrate solution that 0.069ml concentration is 1mol/L, the quality that makes contained cerium is 0.01% of isopropyl titanate and hydronium(ion) oxidation lithium gross mass, and cerous nitrate is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, B solution is slowly added in A solution, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, and the baking oven that then is placed in 160 ℃ of conditions reacted 24 hours, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, wash to pH=7 with deionized water, drying obtains Li under 60 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 2 hours under nitrogen atmosphere, 700 ℃ of conditions, products therefrom namely gets nanoscale Li 4Ti 5O 12/ Ce material.
Adopt the Rigaku D of company the max-2200X x ray diffractometer x sample is carried out material phase analysis (CuK αRadiation, 40kV, 200mA, go on foot wide 0.02 °, 8 °/min of sweep speed, sweep limits (2 θ) is 10 °-80 °, as Fig. 1; Adopt its pattern of S-4800 type sem observation, as Fig. 2.
Be to mix at 80: 10: 10 according to active material, super conductive carbon black (Super P), binding agent Kynoar (PVDF) mass ratio, film into the approximately electrode film of 0.15mm of thickness with the wet film preparing device, 120 ℃ of dryings are 24 hours under vacuum, be cut into slicing machine the electrode slice that diameter is 12mm, weigh and the accurate quality of calculated activity material.As to electrode and reference electrode, Clegard2500 makes barrier film with metal lithium sheet, and the EC+DMC of 1mol/L LiPF6 (volume ratio 1: 1) solution is electrolyte, is assembled into 2016 type button cells in being full of the glove box of argon gas.
Material of the present invention is by test, and its cycle performance curve under different multiplying is seen Fig. 3, and under the 0.1C multiplying power, first discharge specific capacity reaches 200mAhg-1, higher than pure lithium titanate material.Specific capacity under the 10C multiplying power is 140mAhg-1.Fig. 4 is the prepared first charge-discharge platform test curve of lithium titanate material under 0.1C, and it shows that charge and discharge platform is obvious.
Embodiment 3: the present embodiment provides lithium ion secondary battery cathode material lithium titanate of a kind of cerium doping vario-property and preparation method thereof, and with embodiment 1,2 basic identical, its difference is, it comprises the following steps:
(1) measure the 10g amorphous titania, add in the 100ml deionized water, make dispersion liquid A;
(2) measure the 10.63g lithium acetate, with the ratio of the described amorphous titania amount of substance of step (1) be 1: 1.2, be scattered in the 100ml deionized water;
(3) measure the cerous nitrate solution that 0.428ml concentration is 1mol/L, the quality that makes contained cerium is 0.5% of amorphous titania and lithium acetate gross mass, and cerous nitrate solution is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, and the baking oven that then is placed in 160 ℃ of conditions reacts 10h, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with the deionized water washing, drying obtains Li under 60 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 5h under nitrogen atmosphere, 600 ℃ of conditions, products therefrom namely gets nanoscale Li 4Ti 5O 12/ Ce material.
By the material that this method prepares, under the 0.1C multiplying power, specific discharge capacity reaches 195mAhg -1
Embodiment 4: the present embodiment provides lithium ion secondary battery cathode material lithium titanate of a kind of cerium doping vario-property and preparation method thereof, its method and embodiment 1,2,3 basic identical, and its difference is, it comprises the following steps:
(1) measure the 100g anatase titanium dioxide, add in the 500ml deionized water, make dispersion liquid A;
(2) measure the 50g lithium acetate, with the ratio of the described anatase titanium dioxide amount of substance of step (1) be 1: 1.05, be scattered in the 500ml deionized water;
(3) measure the cerous nitrate solution that 6ml concentration is 1mol/L, the quality that makes contained cerium is 0.7% of anatase titanium dioxide and lithium acetate gross mass, and cerous nitrate solution is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, and the baking oven that then is placed in the 160C condition reacts 18h, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with the deionized water washing, drying obtains Li under 60 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 3h under nitrogen atmosphere, 850 ℃ of conditions, products therefrom namely gets nanoscale Li 4Ti 5O 12/ Ce material.
By the material that this method prepares, under the 0.1C multiplying power, specific discharge capacity reaches 190mAhg-1.
Embodiment 5: the present embodiment provides lithium ion secondary battery cathode material lithium titanate of a kind of cerium doping vario-property and preparation method thereof, its method and embodiment 1,2,3,4 basic identical, and its difference is, it comprises the following steps:
(1) measure 402g acetic acid titanium, add in the 500ml deionized water, make dispersion liquid A;
(2) measure the 85g lithium acetate, with the ratio of the described acetic acid titanium of step (1) amount of substance be 1: 1.2, be scattered in the 500ml deionized water;
(3) measure the solution of cerium chloride by oxidation that 1.37ml concentration is 1mol/L, the quality that makes contained cerium is 0.2% of acetic acid titanium and lithium acetate gross mass, and solution of cerium chloride by oxidation is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, and the baking oven that then is placed in 200 ℃ of conditions reacts 24h, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with the deionized water washing, drying obtains Li under 60 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 3h under nitrogen atmosphere, 800 ℃ of conditions, products therefrom namely gets nanoscale Li 4Ti 5O 12/ Ce material.
By the material that this method prepares, under the 0.1C multiplying power, specific discharge capacity reaches 198mAhg -1
Comparative Examples: the present embodiment provides a kind of preparation method of pure lithium ion secondary battery cathode material lithium titanate, and it comprises the following steps:
(1) measure the 28.46ml isopropyl titanate, splash in the 100ml deionized water, make dispersion liquid A;
(2) ratio that measures 3.7g hydronium(ion) oxidation lithium and the described isopropyl titanate amount of substance of step (1) is 1: 1.1, is scattered in and makes dispersion liquid B in the 100ml deionized water;
(3) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(4) reactant mixture that step (3) is made is poured in the pyroreaction still, and the baking oven that then is placed in 100 ℃ of conditions reacts 10h, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with the deionized water washing, drying obtains Li under 60 ℃ of conditions 4Ti 5O 12Presoma;
(5) with the presoma of step (4) gained sintering 3h under nitrogen atmosphere, 800 ℃ of conditions, products therefrom namely gets pure lithium titanate material.
To pure lithium titanate material test comparison obtained above, can draw, this pure lithium titanate electrochemistry cycle performance is compared with the lithium titanate material of doped with cerium provided by the invention, the lithium titanate material of doped with cerium has obviously improved the specific capacity under the different multiplying, has improved the conservation rate of capacity.
But the above is only better possible embodiments of the present invention, is not to limit to the scope of the claims of the present invention, therefore the equivalent structure that all utilizations specification of the present invention and accompanying drawing content are done changes, all is included in protection scope of the present invention.

Claims (5)

1. the lithium ion secondary battery cathode material lithium titanate of a cerium doping vario-property, is characterized in that, it is made by following component: titanium source, lithium source and cerium source; Realize the even distribution of cerium in nano lithium titanate by original position is compound, wherein cerium shared part by weight in composite negative pole material is 0.01～1%, and lithium titanate shared part by weight in composite negative pole material is 99～99.99%.
2. the lithium ion secondary battery cathode material lithium titanate of cerium doping vario-property according to claim 1, it is characterized in that, described titanium source is titanium sulfate, butyl titanate, isopropyl titanate, metatitanic acid, amorphous titania, the business anatase titanium dioxide, one or more in rutile titanium dioxide.
3. the lithium ion secondary battery cathode material lithium titanate of cerium doping vario-property according to claim 1, is characterized in that, described lithium source is one or more in lithia, lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium chloride, lithium nitrate.
4. the lithium ion secondary battery cathode material lithium titanate of cerium doping vario-property according to claim 1, it is characterized in that, described cerium source is one or more in cerium oxide, cerous carbonate, cerium hydroxide, cerous acetate, cerium oxalate, cerium chloride, cerous nitrate, comprise cerium bromide.
One of according to claim 1 to 4 described cerium doping vario-property the preparation method of lithium ion secondary battery cathode material lithium titanate, it is characterized in that, it comprises the following steps:
(1) measure the titanium source, add in deionized water, make dispersion liquid A;
(2) measuring ratio with the described titanium of step (1) source amount of substance is 1: 1.0～1.2 lithium source, is scattered in deionized water;
(3) measure the cerium source, the quality that makes contained cerium is 0.01～1% of titanium source and lithium source gross mass, and the cerium source is added in the dispersion liquid that step (2) makes, and makes dispersion liquid B;
(4) under magnetic agitation, the B dispersion liquid is slowly added in the A dispersion liquid, stir 30min, obtain reactant mixture;
(5) reactant mixture that step (4) is made is poured in the pyroreaction still, then the baking oven that is placed in 120～200 ℃ of conditions reacted 5～48 hours, after reaction finishes, naturally cool to room temperature, then carry out suction filtration, with deionized water or ethanol washing, drying obtains Li under 60～120 ℃ of conditions 4Ti 5O 12/ Ce presoma;
(6) with the presoma of step (5) gained sintering 1～5 hour under nitrogen atmosphere, 400～1000 ℃ of conditions, products therefrom is nanoscale Li 4Ti 5O 12/ Ce material.
CN2012105792991A 2012-12-27 2012-12-27 Cerium-doped modified lithium titanate negative material of lithium ion secondary battery and preparation method thereof Pending CN103107323A (en)

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Cited By (6)

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CN104868111A (en) * 2015-03-27 2015-08-26 陕西科技大学 Preparation method of Ce doped Li4Ti5O12 lithium ion battery cathode material
WO2017103641A1 (en) * 2015-12-18 2017-06-22 Saft Use of electrochemical cells containing a lithiated titanate oxide negative active material for low earth orbit applications
CN107093521A (en) * 2017-05-08 2017-08-25 华北电力大学（保定） A kind of Ce/C composites, its preparation method and its application
CN109867796A (en) * 2019-01-31 2019-06-11 沈阳工业大学 The preparation method of Ce-Li-MOF lithium ion battery negative material and its application in terms of preparing lithium ion battery
CN113471426A (en) * 2021-06-29 2021-10-01 江西瑞马新能源材料技术有限公司 Solid-state silicon composite lithium battery
CN114551858A (en) * 2022-03-01 2022-05-27 深圳博磊达新能源科技有限公司 Lithium titanate composite material and preparation method thereof

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CN102054963A (en) * 2010-07-22 2011-05-11 中信国安盟固利动力科技有限公司 Titanium acid lithium battery cathode material containing rare metal elements
CN102610824A (en) * 2012-03-26 2012-07-25 上海大学 Preparation method of lithium titanate (Li4Ti5O12)/Ag composite lithium-ion negative electrode materials

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WO2008067677A1 (en) * 2006-12-07 2008-06-12 Phostech Lithium Inc. A method for preparing a particulate cathode material, and the material obtained by said method
CN102054963A (en) * 2010-07-22 2011-05-11 中信国安盟固利动力科技有限公司 Titanium acid lithium battery cathode material containing rare metal elements
CN102610824A (en) * 2012-03-26 2012-07-25 上海大学 Preparation method of lithium titanate (Li4Ti5O12)/Ag composite lithium-ion negative electrode materials

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868111A (en) * 2015-03-27 2015-08-26 陕西科技大学 Preparation method of Ce doped Li4Ti5O12 lithium ion battery cathode material
WO2017103641A1 (en) * 2015-12-18 2017-06-22 Saft Use of electrochemical cells containing a lithiated titanate oxide negative active material for low earth orbit applications
CN108604679A (en) * 2015-12-18 2018-09-28 Saft公司 Including the electrochemical cell of lithiumation titanate oxide negative electrode active material is used for the purposes of LEO application
RU2705568C1 (en) * 2015-12-18 2019-11-08 Сафт Use of electrochemical cells containing a negative active material based on lithium titanium oxide or titanate, for low-earth orbit applications
CN108604679B (en) * 2015-12-18 2022-03-22 Saft公司 Use of electrochemical cells comprising lithiated titanate oxide negative active materials for near earth rail applications
CN107093521A (en) * 2017-05-08 2017-08-25 华北电力大学（保定） A kind of Ce/C composites, its preparation method and its application
CN107093521B (en) * 2017-05-08 2020-10-20 华北电力大学（保定） Ce/C composite material, preparation method and application thereof
CN109867796A (en) * 2019-01-31 2019-06-11 沈阳工业大学 The preparation method of Ce-Li-MOF lithium ion battery negative material and its application in terms of preparing lithium ion battery
CN109867796B (en) * 2019-01-31 2021-08-10 沈阳工业大学 Preparation method of Ce-Li-MOF lithium ion battery negative electrode material and application of Ce-Li-MOF lithium ion battery negative electrode material in preparation of lithium ion battery
CN113471426A (en) * 2021-06-29 2021-10-01 江西瑞马新能源材料技术有限公司 Solid-state silicon composite lithium battery
CN114551858A (en) * 2022-03-01 2022-05-27 深圳博磊达新能源科技有限公司 Lithium titanate composite material and preparation method thereof

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Application publication date: 20130515