CN105789607A - Preparation method of lithium titanate anode material doped with rare earth - Google Patents

Preparation method of lithium titanate anode material doped with rare earth Download PDF

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CN105789607A
CN105789607A CN201610306113.3A CN201610306113A CN105789607A CN 105789607 A CN105789607 A CN 105789607A CN 201610306113 A CN201610306113 A CN 201610306113A CN 105789607 A CN105789607 A CN 105789607A
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rare earth
preparation
lithium
lithium compound
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闫慧
王晓霞
刘云颖
王正德
郭贵宝
白宇辰
海波
马力通
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Inner Mongolia University of Science and Technology
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    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

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Abstract

The invention belongs to the field of lithium ion secondary battery materials and discloses a preparation method of a lithium titanate anode material doped with rare earth (La, Ce, Pr, Nd, Sm, Dy, Gd and the like). The preparation method comprises the following steps of mixing titanium dioxide with an aqueous solution of a lithium compound; performing a hydrothermal reaction at the temperature of 120DEG C for 10 hours; drying, grinding and then sintering an obtained intermediate at high temperature of 650DEG C for 4 hours to obtain a lithium titanate Li4Ti(5-x)RExO12(x is equal to 0.01 to 0.3) material doped with rare earth. The tap density of the Li4Ti(5-x)RExO12 material prepared by the preparation method disclosed by the invention reaches 1.4 to 2.0g/cm<3>; the Li4Ti(5-x)RExO12 material has excellent electrochemical property; first discharge specific capacity is as high as 172mAh/g, the capacity attenuation rate of each one cycle on average is smaller than 0.05 percent, and 10 C rate discharge specific capacity still reaches 145mAh/g, so the Li4Ti(5-x)RExO12 material is an ideal anode material for a high-power lithium ion power battery; in addition, the preparation method is simple and practical, low in cost and suitable for industrial scale production, and has a broad application prospect.

Description

A kind of preparation method of rare earth doped lithium titanate anode material
Technical field
The invention belongs to lithium rechargeable battery Material Field, be specifically related to the preparation method of a kind of rare earth doped lithium titanate anode material, can be as cathode material for lithium-ion power battery.
Background technology
Automobile industry is the pillar industry that national economy is important, is also the significant industry embodying national competitiveness.China has become the first in the world automobile production and marketing state, the longest one period China's automobile volume of production and marketing also will keep quick growth, expect the year two thousand twenty automobile pollution and will reach 2.5 hundred million, by current automobile fuel ecomomy horizontal estimated, fuel oil for vehicles Year's consumption will break through 400,000,000 tons, and the energy security thus brought and environmental problem will be more prominent.Therefore, greatly develop energy-conservation and new-energy automobile, accelerate the industrialization process of propulsion energy-saving and new-energy automobile, be to successfully manage the energy and environment challenge, it is achieved the inevitable choice of Chinese Auto Industry sustainable development.Thus need to research and develop high-power, high-energy, long-life, high security, low cost and eco-friendly electrokinetic cell.Lithium rechargeable battery has the advantages such as good cycle, energy density is high, voltage platform is high it is considered to be most possibly used as the electrokinetic cell of electric automobile.The research and development of lithium-ion-power cell is most important part in " 13 " Energy efficiency in planning and new-energy automobile major project, become state key and support and encourage the project of development, also it is the focus of whole world research and development, so research and development high-performance, highly secure lithium ion dynamic battery are the most necessary simultaneously.At present, the negative material of business-like lithium ion battery is mainly carbon negative pole material, but its characteristic that first charge-discharge irreversible capacity is higher, safety is low, cycle performance is poor, not being suitable for electric automobile etc. needs the equipment of high current charge-discharge.It is long that lithium titanate has service life, and overcharging resisting is crossed and put the feature good with security performance, meets the demand of high-power discharge and recharge.
Pure spinelle Li4Ti5O12Electronics and the ionic conductivity of material are relatively low, and respectively 10-13 S·cm-1With 10-9~10-13 cm2·s-1, therefore many researcheres pass through conventional high-temperature solid phase method to Li4Ti5O12Carrying out rear-earth-doped improvement, the method is difficult to ensure that batch mixing is uniform, and resulting materials is more than under 800 DEG C of high temperature, could prepare more than 15 hours heat treatments, and resulting materials chemical property is poor.Such as Chinese patent CN 101456581 A have reported by traditional segmented high-temperature Solid phase synthesis the lithium titanate material containing rare earth element, materials synthesis complex steps in the embodiment of this patent report, heat treatment temperature are high, the time is long, and the lithium titanate material first discharge specific capacity of gained doped with rare-earth elements only has 163 MAh/g, repeatedly after charge and discharge cycles, capacity attenuation is very fast.Therefore researchers are by the material of the method synthesizing blender transition metal metatitanic acid lithiums such as sol-gel process, microemulsion method, solvent-thermal method, electrospray deposition.These methods can prepare the material of size tunable, but its complex steps, chemical time are longer and raw materials used environment are had pollution, are not easy to industrialized production.And it mostly is nanoscale by the particle diameter of said method resulting materials, and the less energy density that result in battery of the tap density of nano material is relatively low, the specific surface area that nano material is bigger makes again reactivity higher, may result in material capacity in charge and discharge process and declines rapidly.Chinese patent CN 102328952 B report a kind of method preparing spherical lithium titanate material, the spherical micron-sized lithium titanate material of pattern rule has been obtained by the method, but resulting materials battery capacity decay during high rate charge-discharge is very fast, owing to resulting materials particle diameter is the least, tap density is relatively low, is unfavorable for the raising of material energy densities.By patent CN Method disclosed in 102328952 B, it was predicted that use the TiO of big particle diameter2Raw material can obtain the lithium titanate material of big particle diameter, but owing to the low conductivity of lithium titanate self causes Li under its big particle diameter+Can not quickly embed in positive electrode so that it is can not large-scale application.
Summary of the invention
The present invention is primarily to solve the pure low electronics of spinel lithium titanate material and low ionic conductivity, and pass through the shortcoming that liquid phase method gained lithium titanate material particle diameter is less, complex steps, cost are high, provide a kind of by using low price raw material, the lithium titanate anode material of synthesizing blender rare earth under short period and lower temperature, chemical formula is Li4Ti5-xRExO12(0.01≤x≤0.30), resulting materials has tap density height, specific discharge capacity height, high rate performance excellent characteristics.
For realizing above-mentioned technical purpose, the present invention is accomplished by:
The preparation method of a kind of rare earth doped lithium titanate anode material, rare earth doped lithium titanate material prepared by the method is ion secondary battery cathode material lithium, the Li of synthesis4Ti5-xRExO12Containing rare earth element in material, its content is 0.01 ~ 0.3 mol%.
The preparation method of a kind of rare earth doped lithium titanate anode material, comprises the steps:
1) preparation lithium concentration is the lithium compound aqueous solution of 0.5 ~ 5 mol/L；
2) Li is pressed4Ti5-xRExO12Middle thing mass ratio, takes x=0.01 ~ 0.30, by uniform to titanium dioxide, rare earth compound and lithium compound aqueous solution, in 120 DEG C of hydro-thermal reactions 10 hours, obtains precursor product；
3) gained presoma being dried and ground 30 ~ 90 minutes, then 650 DEG C of constant temp. heatings process 4 hours, obtain Li4Ti5-xRExO12 material.
Further, high temperature products obtained therefrom is cooled down, pulverizes, sieves, obtain the rare earth doped lithium titanate material of finished product.
In above-mentioned preparation method, lithium salt compound described in step 1) is one or more in Lithium hydrate, lithium carbonate or lithium nitrate lithium compound, preferably lithium nitrate.
Above-mentioned steps 2) described rare earth compound is the one in rare earth oxide, carbonated rare earth or nitric acid rare earth compound, the number of rear-earth-doped amount determines the size of resulting materials particle diameter, preferably carbonated rare earth.
Above-mentioned steps 2) described titanium dioxide is that 4:5 is preferable with the ratio of the amount of the material of Li/ (RE+Ti) in the mixed material of lithium compound and rare earth compound, the doping of rare earth is 0.01 ~ 0.3 mol%, preferably the doping of rare earth be the doping of 0.01 ~ 0.25 mol%, most preferably rare earth be 0.05 ~ 0.2 Mol%, it is contemplated that the volatility of lithium compound under hot conditions, can suitably increase the consumption of lithium compound but no more than 4 wt%, the consumption preferably increasing lithium compound is 2 ~ 3%.
Above-mentioned steps 3) atmosphere of high-temperature process is not particularly limited, can be air atmosphere or inert atmosphere, sintering enormously simplify process conditions the most in atmosphere.
The invention have the advantages that
1. utilize common raw material, through less step, it is not necessary to long-time high-temperature process can synthesize rare earth doped lithium titanate material.
2. the Li prepared by4Ti5-xRExO12The tap density of material reaches 1.4 ~ 2.0g/cm3.This material is detected as pure spinel structure through X-ray powder diffractometer (XRD), exists mutually without other non-spinelle impurity；Scanned ultramicroscope (SEM) detects, this Li4Ti5-xRExO12The particle diameter of material is gradually increased with the increase of rear-earth-doped amount, and tap density increases the most therewith.
3. the Li prepared by4Ti5-xRExO12Material has excellent chemical property, including cycle performance and high-multiplying-power discharge performance, is preferable high power lithium ion power battery negative material.Under 0.2C current discharge, first discharge specific capacity is more than 170mAh/g, and average every circulation primary capacity attenuation rate is less than 0.5 ‰；145mAh/g is still had with 10C multiplying power discharging specific capacity.
4. the present invention prepares rare earth doped lithium titanate Li4Ti5-xRExO12The method simple practical of material, low cost, it is suitable for industrial-scale production.
Accompanying drawing explanation
Fig. 1 is embodiment 1(120 DEG C hydrothermal temperature) and 1(100 DEG C of hydrothermal temperature of comparative example) Li that synthesizes4Ti4.95La0.05O12The X-ray powder diagram of material.
Fig. 2 is embodiment 1(120 DEG C hydrothermal temperature) and 1(100 DEG C of hydrothermal temperature of comparative example) Li that synthesizes4Ti4.95La0.05O12The specific discharge capacity circulation figure of material.
Detailed description of the invention
Below by embodiment, technical scheme is further described in detail.
Embodiment 1
1. Li4Ti4.95La0.05O12The synthesis of material
Compound concentration is the lithium hydroxide aqueous solution of 5 mol/L.39.5 grams of anatase titanium dioxides and 1.14 grams of lanthanum carbonates are weighed in hydrothermal reaction kettle according to stoichiometric proportion, measure afterwards 0.08 liter preparation lithium hydroxide aqueous solution in hydrothermal reaction kettle, be uniformly mixed in the baking oven being placed on 120 DEG C reaction 10 hours.Hydro-thermal reaction products therefrom is taken out, is dried and transferred in alumina crucible.Crucible is placed in Muffle furnace, is warming up to 650 DEG C with the speed of 6 DEG C/min, constant temperature 6 hours, stop heating, in stove, naturally cool to room temperature, obtain Li4Ti4.95La0.05O12Material product.Test through XRD, show the product that material is single spinel structure, as shown in Figure 1；Observing through SEM, product particle smooth surface, densification, in spinel-type, the tap density of material is 1.4 g/cm3。
2. Li4Ti4.95La0.05O12The chemical property of material
The Li that will synthesize4Ti4.95La0.05O12, acetylene black and electrically conductive graphite, the binding agent polyvinylidene fluoride PVDF wherein acetylene black of 90:4:6(in mass ratio and electrically conductive graphite and account for total proportion 4%) mix homogeneously, be coated on aluminium foil, be cut into pole piece after drying.By electrolyte LiPF6Salt is dissolved in the mixed solution of the ethylene carbonate (EC)/dimethyl carbonate (DMC) that volume ratio is 1:1 and forms the electrolyte that concentration is 1 mol/L, with lithium metal for electrode, in the vacuum glove box of full argon, it is assembled into R2032 button cell, carries out electrochemical property test.Charging/discharging voltage is 1.0 ~ 2.5RE, and under 0.2C current discharge, first discharge specific capacity reaches 172mAh/g, and average every circulation primary capacity attenuation rate is less than 0.5 ‰；Still having 144mAh/g with 10C multiplying power discharging specific capacity, electrochemical property test the results are shown in Table 1.
Embodiment 2
1. Li4Ti4.9La0.1O12The synthesis of material
Compound concentration is the lithium hydroxide aqueous solution of 5 mol/L.Weigh 39.1 grams of anatase titanium dioxides and 2.29 grams of lanthanum carbonates in hydrothermal reaction kettle according to stoichiometric proportion, measure the lithium hydroxide aqueous solution of 0.08 liter of preparation afterwards in hydrothermal reaction kettle, be uniformly mixed in the baking oven being placed on 120 DEG C reaction 10 hours.Hydro-thermal reaction products therefrom is taken out, is dried and transferred in alumina crucible.Crucible is placed in Muffle furnace, is warming up to 650 DEG C with the speed of 6 DEG C/min, constant temperature 6 hours, stop heating, in stove, naturally cool to room temperature, obtain Li4Ti4.9La0.1O12Material product.Test through XRD, show the product that material is single spinel structure；Observing through SEM, product particle smooth surface, densification, in spinel-type；The tap density of material is 1.6 g/cm3。
2. Li4Ti4.9La0.1O12The chemical property of material
According to the condition assembled battery that embodiment 1 is identical.Charging/discharging voltage is 1.0 ~ 2.5V, and under 0.2C current discharge, first discharge specific capacity is at 166mAh/g, and average every circulation primary capacity attenuation rate is less than 0.8 ‰, with 10C multiplying power discharging specific capacity as 137mAh/g.
Embodiment 3
1. Li4Ti4.95Ce0.05O12The synthesis of material
Compound concentration is the lithium hydroxide aqueous solution of 5 mol/L.39.5 grams of anatase titanium dioxides and 1.15 grams of cerous carbonates are weighed in hydrothermal reaction kettle according to stoichiometric proportion, measure afterwards 0.08 liter preparation lithium hydroxide aqueous solution in hydrothermal reaction kettle, be uniformly mixed in the baking oven being placed on 120 DEG C reaction 10 hours.Hydro-thermal reaction products therefrom is taken out, is dried and transferred in alumina crucible.Crucible is placed in Muffle furnace, is warming up to 650 DEG C with the speed of 6 DEG C/min, constant temperature 6 hours, stop heating, in stove, naturally cool to room temperature, obtain Li4Ti4.95Ce0.05O12Material product.Testing through XRD, show the product that material is single spinel structure, the tap density of material is 1.41 g/cm3。
2. Li4Ti4.95Ce0.05O12The chemical property of material
According to the condition assembled battery that embodiment 1 is identical.Charging/discharging voltage is 1.0 ~ 2.5V, and under 0.2C current discharge, first discharge specific capacity is at 171mAh/g, and average every circulation primary capacity attenuation rate is less than 0.4 ‰, and with 10C multiplying power discharging specific capacity as 148mAh/g, electrochemical property test the results are shown in Table 2.
Embodiment 4
1. Li4Ti4.9Ce0.1O12The synthesis of material
Compound concentration is the lithium hydroxide aqueous solution of 5 mol/L.Weigh 38.3 grams of anatase titanium dioxides and 2.3 grams of cerous carbonates in hydrothermal reaction kettle according to stoichiometric proportion, measure the lithium hydroxide aqueous solution of 0.08 liter of preparation afterwards in hydrothermal reaction kettle, be uniformly mixed in the baking oven being placed on 120 DEG C reaction 10 hours.Hydro-thermal reaction products therefrom is taken out, is dried and transferred in alumina crucible.Crucible is placed in Muffle furnace, is warming up to 650 DEG C with the speed of 6 DEG C/min, constant temperature 6 hours, stop heating, in stove, naturally cool to room temperature, obtain Li4Ti4.9Ce0.1O12Material product.Testing through XRD, show the product that material is single spinel structure, the tap density of material is 1.6 g/cm3。
2. Li4Ti4.9Ce0.1O12The chemical property of material
According to the condition assembled battery that embodiment 1 is identical.Charging/discharging voltage is 1.0 ~ 2.5V, and under 0.2C current discharge, first discharge specific capacity is at 166mAh/g, and average every circulation primary capacity attenuation rate is less than 1 ‰, with 10C multiplying power discharging specific capacity as 139mAh/g.
Comparative example 1
1. Li4Ti4.95La0.05O12The synthesis of material
Substitute the heat treatment time of 120 DEG C with the hydrothermal temperatures of 100 DEG C, other condition is same as in Example 1.Test through XRD, show that material is containing La2O3The Li of the single spinel structure of impurity phase4Ti4.95La0.05O12Material, the tap density of material is 1.3g/cm3。
2. Li4Ti4.95La0.05O12The chemical property of material
According to the condition assembled battery that embodiment 1 is identical.Charging/discharging voltage is 1.0 ~ 2.5 V, under 0.2C current discharge, specific discharge capacity is at 145mAh/g, and average every circulation primary capacity attenuation rate is less than 1%.
Comparative example 2
1. Li4Ti4.95Ce0.05O12The synthesis of material
Substitute the heat treatment temperature of 650 DEG C with the heat treatment temperatures of 800 DEG C, other condition is same as in Example 3.Test through XRD, show that material is containing CeO2And TiO2The Li of the spinel structure of impurity phase4Ti4.95Ce0.05O12, the tap density of material is 1.2 g/cm3。
2. Li4Ti4.95Ce0.05O12The chemical property of material
According to the condition assembled battery that embodiment 1 is identical.Charging/discharging voltage is 1.0 ~ 2.5 V, under 0.2C current discharge, specific discharge capacity is at 140mAh/g, and average every circulation primary capacity attenuation rate is 2%.

Claims (10)

1. a rare earth doped lithium titanate anode material preparation method, it is characterised in that the Li of synthesis4Ti5-xRExO12Material Rare-Earth Content is 0.01 ~ 0.3 mol%.
A kind of rare earth doped lithium titanate anode material preparation method the most as claimed in claim 1, comprises the steps:
1) preparation lithium concentration is the lithium compound aqueous solution of 0.5 ~ 5 mol/L；
2) Li is pressed4Ti5-xRExO12Middle thing mass ratio, takes x=0.01 ~ 0.3, by uniform to titanium dioxide, rare earth compound and lithium compound aqueous solution, in 120 DEG C of hydro-thermal reactions 10 hours, obtains precursor product；
3) being dried by gained presoma and ball milling 30 ~ 90 minutes, then 650 DEG C of high-temperature heat treatment 4 hours, obtain Li4Ti5-xRExO12 material.
3. preparation method as claimed in claim 2, it is characterised in that lithium compound described in step 1) is inorganic lithium compound, one or more mixing in Lithium hydrate, lithium carbonate or lithium nitrate lithium compound.
4. preparation method as claimed in claim 2, it is characterised in that step 2) described rare earth compound is the one in rare earth oxide, carbonated rare earth or nitric acid rare earth compound, rear-earth-doped amount number determine the size of resulting materials particle diameter.
5. preparation method as claimed in claim 2, it is characterised in that step 2) described titanium dioxide, lithium compound and rare earth compound mixed material in the ratio of amount of material of Li/ (RE+Ti) be 4:5, the doping of rare earth is 0.01 ~ 0.3 Mol%, can suitably increase the consumption of lithium compound but no more than 4 wt%, the consumption preferably increasing lithium compound is 2 ~ 3%.
6. preparation method as claimed in claim 2, it is characterised in that the doping of described rare earth is 0.05 ~ 0.25 mol%；In view of the volatility of lithium compound under hot conditions, can suitably increase the consumption of lithium compound but no more than 4 wt%, the consumption preferably increasing lithium compound is 2 ~ 3%.
7. preparation method as claimed in claim 2, it is characterized in that, the doping of described rare earth is 0.1 ~ 0.2 mol%, it is contemplated that the volatility of lithium compound under hot conditions, can suitably increase the consumption of lithium compound but no more than 4 wt%, the consumption preferably increasing lithium compound is 2 ~ 3%.
8. preparation method as claimed in claim 2, it is characterised in that in step 3), high-temperature heat treatment is carried out in atmosphere.
9. preparation method as claimed in claim 1 or 2, it is characterised in that described rare earth is rare earth oxide, carbonated rare earth or nitric acid rare earth.
10. preparation method as claimed in claim 9, it is characterised in that rare earth oxide REO includes: containing the oxide of La, Ce, Pr, Nd, Sm, Dy or Gd rare earth element；Carbonated rare earth RECO3Including: containing the carbonate of La, Ce, Pr, Nd, Sm, Dy or Gd rare earth element；Nitric acid rare earth RENO3Including: containing the nitrate of La, Ce, Pr, Nd, Sm, Dy or Gd rare earth element.
CN201610306113.3A 2016-05-10 2016-05-10 Preparation method of lithium titanate anode material doped with rare earth Pending CN105789607A (en)

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CN106299349B (en) * 2016-08-26 2018-09-07 浙江长兴金太阳电源有限公司 Lithium ion battery adulterates the preparation method of lithium nickelate material with holmium
CN106299337B (en) * 2016-08-26 2018-09-07 浙江长兴金太阳电源有限公司 A kind of preparation method of the terbium doped lithium manganate material of lithium ion battery
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CN107942256B (en) * 2017-11-15 2021-01-05 内蒙古科技大学 Battery performance prediction method using phosphorus alkene as negative electrode material
CN108906026A (en) * 2018-08-07 2018-11-30 吉林大学 Lanthanum cerium codoping titanium oxide material and preparation method based on mischmetal carbonate
CN108906026B (en) * 2018-08-07 2021-04-16 吉林大学 Lanthanum-cerium co-doped titanium oxide material based on mixed rare earth carbonate and preparation method thereof
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CN112436119A (en) * 2020-11-24 2021-03-02 张金龙 Porous nano TiO2Coated SnO2Lithium ion battery cathode material and preparation method thereof
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