CN106450262A - Hollow-sphere-shaped lithium titanate anode material and preparation method and application thereof - Google Patents
Hollow-sphere-shaped lithium titanate anode material and preparation method and application thereof Download PDFInfo
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- CN106450262A CN106450262A CN201610966701.XA CN201610966701A CN106450262A CN 106450262 A CN106450262 A CN 106450262A CN 201610966701 A CN201610966701 A CN 201610966701A CN 106450262 A CN106450262 A CN 106450262A
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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
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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
- 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
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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
- H01M4/13—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
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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
- H01M4/13—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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a hollow-sphere-shaped lithium titanate anode material and a preparation method and application thereof. The preparation method comprises the following steps: dispersing spherical silicon dioxide in a mixed solution of anhydrous ethanol and water, then adding organic titanate, and magnetically stirring the mixed solution for 30-40 minutes; in a stirring process of the solution, dropwise adding acid into the solution by using an acid burette until gel is formed; drying to form a black fluffy precursor; calcining the precursor in a muffle furnace to form a SiO2@TiO2 core-shell structure; and fully mixing the SiO2@TiO2 core-shell structure with lithium salt, and calcining to form Li2SiO3@Li4Ti5O12; and dissolving the Li2SiO3@Li4Ti5O12 in a hot alkaline solution to form the hollow-sphere-shaped Li4Ti5O12. The hollow-sphere-shaped lithium titanate has large specific surface area, and then the electrochemical performance of the material can be improved, the specific discharge capacity of the material is about 175 mAh/g, after repeated circulating, capacity loss is quite low, and the circulating performance is stable.
Description
Technical field
The present invention designs a kind of preparation method of lithium cell negative pole material, and more particularly to a kind of hollow ball pattern lithium titanate is born
Pole material and preparation method and application.
Background technology
With less, lighter and the electronics of higher performance and developing rapidly of communication apparatus, people carry to for these equipment
The battery performance of power supply source especially proposes higher and higher requirement to specific energy.But, the lithium-ion electric of commercialization at present
The specific capacity of pond and MH/Ni battery has been difficult to continue to improve.Therefore, the battery higher in the urgent need to developing specific energy.Lithium from
Sub- secondary cell has been widely used for mobile communication, notebook computer, video camera, photograph as high-energy-density electrochmical power source
The fields such as machine, portable instrument, develop rapidly and become one of currently the most important ones secondary cell.Lithium ion battery is as
The green high-capacity accumulator of a new generation, developed rapidly in early 1990s, and lithium ion battery is because its voltage is high, energy
Density is high, have extended cycle life, gain great popularity the advantages of environmental pollution is little.At present, business-like lithium ion battery negative material is big
Majority adopts carbon negative pole material, but carbon negative pole material has some defects:React with electrolyte in discharge process first
Formed surface passivated membrane, lead to electrolyte consumption and first coulombic efficiency relatively low;The electrode potential phase of carbon electrode and lithium metal
Closely, in battery overcharge it would still be possible in carbon electrodes precipitating metal lithium, and dendrite can be formed and causes short circuit, cause safety
Problem etc..Finding new ion cathode material lithium becomes the focus of research.The lithium titanate of spinel-type is a kind of zero strain material
Material, good cycle, do not react with electrolyte, charging/discharging voltage platform compare steadily, safety is higher, cheap and compares
Easily prepare, be very promising power-type lithium ion battery negative material.Meanwhile, this material there is also some shortcomings,
Li4Ti5O12Electrical conductivity very low, almost insulate, the poor-performing under high magnification, if be applied to power car, large-scale energy-storage battery
Will be extremely limited in field.Thus, for Li4Ti5O12The shortcoming of material conductivity difference, improves its electrical conductivity and height
The research of high rate performance is particularly important.At present, conventional method of modifying is by its nanorize, cladding or doping, with this
Tentatively to lift electrode performance.Prepare the Li of nanorize4Ti5O12, reduce the size of material granule, shorten Li+Diffusion road
Footpath, reduction Li+Diffusional resistance, slow down the purpose of electrode polarization, the chemical property of material is improve with this, but nanometer
Change granule to be susceptible to reunite in charge and discharge process.Carry out process with discharge and recharge, the chemical property of material can decline.
Content of the invention
For overcoming the deficiencies in the prior art, a kind of preparation method of present invention hollow ball pattern lithium titanate anode material.Empty
The lithium titanate of bulbus cordis pattern has larger specific surface area, can be fully contacted with electrolyte, improves the electrochemistry of material further
Performance.
A kind of preparation method of hollow ball pattern lithium titanate anode material is it is characterised in that the concretely comprising the following steps of the method:
(1)0.05 mol preparing spherical SiO 2 is distributed in dehydrated alcohol and the mixed solution of water, adds 10 mL organic titaniums
Hydrochlorate, by above-mentioned mixed solution magnetic agitation 30~40 min;
(2)During above-mentioned solution stirring, acid acid buret is added dropwise in above-mentioned solution, to formation gel;
(3)Gel is put into 6~8 hs in 200~240 DEG C in convection oven, are dried, form the presoma of black puffy;
(4)Presoma is placed in 600~800 DEG C of calcinings in Muffle furnace, forms SiO2@TiO2Nucleocapsid structure;
(5)By SiO2@TiO2Nucleocapsid structure is sufficiently mixed with lithium salts, and 800~1000 DEG C of calcinings form Li2SiO3@Li4Ti5O12;
(6)By Li2SiO3@Li4Ti5O12It is dissolved in hot alkaline solution, form the Li of hollow ball pattern4Ti5O12.
Described organic titanate is one of butyl titanate, isopropyl titanate or a combination thereof.
The volume ratio of described water and ethanol is 1:(0.1~0.5).
Described acidic materials are one of acetic acid, nitric acid or a combination thereof.
Described lithium salts is lithium nitrate, lithium chloride, lithium acetate, Lithium Citrate de, lithium oxalate, lithium formate, EINECS 212-761-8 or isopropyl
One of lithium alkoxide or a combination thereof.
Described thermokalite is one of Lithium hydrate, sodium hydroxide, potassium hydroxide or a combination thereof.
A kind of hollow ball pattern lithium titanate anode material is it is characterised in that prepare according to any of the above-described methods described.
A kind of hollow ball pattern lithium titanate anode material is as the application of negative electrode of lithium titanate battery material.
The present invention, with preparing spherical SiO 2 as core, hydrolyzes preparation titanium dioxide using organic titanate by sol-gal process
Titanium, with titanium dioxide as shell, obtains SiO2@TiO2, then Li is obtained by lithiumation process2SiO3@Li4Ti5O12, then pass through thermokalite
Corrosion silicate process, finally prepares the Li of hollow ball pattern4Ti5O12, the lithium titanate of hollow ball pattern has larger ratio table
Area, and then the chemical property of material can be improved.
Brief description
Fig. 1 is embodiment 1 Li4Ti5O12The XRD figure of material;
Fig. 2 is embodiment 2 Li4Ti5O12The cycle life performance figure of material.
Specific embodiment
The present invention is described in detail by following instantiation, but protection scope of the present invention is not only restricted to these
Examples of implementation.
Embodiment one:
0.05 mol preparing spherical SiO 2 is distributed in dehydrated alcohol and the mixed solution of water, adds 10 mL metatitanic acid four fourth
Ester, by above-mentioned mixed solution magnetic agitation 30 min;During above-mentioned solution stirring, acetic acid acid buret is dropwise added
Enter in above-mentioned solution, to formation gel;Gel is put into 6 hs in 240 DEG C in convection oven, are dried, form black puffy
Presoma;Presoma is placed in 700 DEG C of calcinings in Muffle furnace, forms SiO2@TiO2Nucleocapsid structure;By SiO2@TiO2Nucleocapsid is tied
Structure is sufficiently mixed with lithium acetate, and 800 DEG C of calcinings form Li2SiO3@Li4Ti5O12;By Li2SiO3@Li4Ti5O12It is dissolved in hot NaOH
In solution, form the Li of hollow ball pattern4Ti5O12.Fig. 1 is hollow ball Li4Ti5O12XRD figure, synthetic product Li4Ti5O12's
XRD schemes the position of each diffraction maximum and relative intensity is all matched with the standard card of Li4Ti5O12.
Embodiment two:
0.05 mol preparing spherical SiO 2 is distributed in dehydrated alcohol and the mixed solution of water, adds 10 mL metatitanic acid isopropyls
Ester, by above-mentioned mixed solution magnetic agitation 30 min;During above-mentioned solution stirring, nitric acid acid buret is dropwise added
Enter in above-mentioned solution, to formation gel;Gel is put into 8 hs in 240 DEG C in convection oven, are dried, form black puffy
Presoma;Presoma is placed in 600 DEG C of calcinings in Muffle furnace, forms SiO2@TiO2Nucleocapsid structure;By SiO2@TiO2Nucleocapsid is tied
Structure is sufficiently mixed with lithium nitrate, and 800 DEG C of calcinings form Li2SiO3@Li4Ti5O12;By Li2SiO3@Li4Ti5O12It is dissolved in hot NaOH
In solution, form the Li of hollow ball pattern4Ti5O12.Fig. 2 is Li4Ti5O12Cycle life performance figure under 1C multiplying power for the material, by
Figure is visible, during 1 C discharge capacity first up to 196 mAh/g, from second stable discharging specific capacity 175 mAh/g, warp
After crossing multiple circulation, capacitance loss also very little, it is demonstrated by stable cycle performance.
Embodiment three:
0.05 mol preparing spherical SiO 2 is distributed in dehydrated alcohol and the mixed solution of water, adds 10 mL metatitanic acid four fourth
Ester, by above-mentioned mixed solution magnetic agitation 30 min;During above-mentioned solution stirring, nitric acid acid buret is dropwise added
Enter in above-mentioned solution, to formation gel;Gel is put into 8 hs in 220 DEG C in convection oven, are dried, form black puffy
Presoma;Presoma is placed in 800 DEG C of calcinings in Muffle furnace, forms SiO2@TiO2Nucleocapsid structure;By SiO2@TiO2Nucleocapsid structure
It is sufficiently mixed with lithium nitrate, 800 DEG C of calcinings form Li2SiO3@Li4Ti5O12;By Li2SiO3@Li4Ti5O12It is dissolved in hot KOH solution
In, form the Li of hollow ball pattern4Ti5O12.
Claims (8)
1. a kind of preparation method of hollow ball pattern lithium titanate anode material is it is characterised in that the concretely comprising the following steps of the method:
(1)0.05 mol preparing spherical SiO 2 is distributed in dehydrated alcohol and the mixed solution of water, adds 10 mL organic titaniums
Hydrochlorate, by above-mentioned mixed solution magnetic agitation 30~40 min;
(2)During above-mentioned solution stirring, acid acid buret is added dropwise in above-mentioned solution, to formation gel;
(3)Gel is put into 6~8 hs in 200~240 DEG C in convection oven, are dried, form the presoma of black puffy;
(4)Presoma is placed in 600~800 DEG C of calcinings in Muffle furnace, forms SiO2@TiO2Nucleocapsid structure;
(5)By SiO2@TiO2Nucleocapsid structure is sufficiently mixed with lithium salts, and 800~1000 DEG C of calcinings form Li2SiO3@Li4Ti5O12;
(6)By Li2SiO3@Li4Ti5O12It is dissolved in hot alkaline solution, form the Li of hollow ball pattern4Ti5O12.
2. according to claim 1 a kind of preparation method of hollow ball pattern lithium titanate anode material it is characterised in that described
Organic titanate be one of butyl titanate, isopropyl titanate or a combination thereof.
3. according to claim 1 a kind of preparation method of hollow ball pattern lithium titanate anode material it is characterised in that described
Water and ethanol volume ratio be 1:(0.1~0.5).
4. according to claim 1 a kind of preparation method of hollow ball pattern lithium titanate anode material it is characterised in that described
Acidic materials be one of acetic acid, nitric acid or a combination thereof.
5. according to claim 1 a kind of preparation method of hollow ball pattern lithium titanate anode material it is characterised in that described
Lithium salts be one of lithium nitrate, lithium chloride, lithium acetate, Lithium Citrate de, lithium oxalate, lithium formate, EINECS 212-761-8 or isopropyl lithium alkoxide
Or a combination thereof.
6. according to claim 1 a kind of preparation method of hollow ball pattern lithium titanate anode material it is characterised in that described
Thermokalite be one of Lithium hydrate, sodium hydroxide, potassium hydroxide or a combination thereof.
7. a kind of hollow ball pattern lithium titanate anode material is it is characterised in that prepare according to the arbitrary methods described of claim 1-6
Obtain.
8. according to claim 7 hollow ball pattern lithium titanate anode material lithium titanate battery as negative material should
With.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108134075A (en) * | 2017-12-07 | 2018-06-08 | 三峡大学 | A kind of sodium titanate microballoon and its application in sodium-ion battery |
CN112467096A (en) * | 2020-10-30 | 2021-03-09 | 安普瑞斯(南京)有限公司 | Negative electrode material, preparation method thereof, electrode and secondary battery |
CN113193181A (en) * | 2021-04-23 | 2021-07-30 | 湖州杉杉新能源科技有限公司 | Pre-lithiated silica composite material, precursor, preparation method and application thereof |
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CN102522536A (en) * | 2011-12-17 | 2012-06-27 | 合肥国轩高科动力能源有限公司 | Template synthesis method of lithium ion negative electrode material lithium titanate |
CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
CN105261748A (en) * | 2015-10-30 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing negative electrode material mono-dispersed nano-crystalline lithium titanate by using nanometer microreactor |
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JP2002324551A (en) * | 2001-04-27 | 2002-11-08 | Titan Kogyo Kk | Titanic acid lithium powder and its use |
WO2007078429A2 (en) * | 2005-12-23 | 2007-07-12 | Uchicago Argonne, Llc. | Electrode materials and lithium battery systems |
CN102522536A (en) * | 2011-12-17 | 2012-06-27 | 合肥国轩高科动力能源有限公司 | Template synthesis method of lithium ion negative electrode material lithium titanate |
CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
CN105261748A (en) * | 2015-10-30 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing negative electrode material mono-dispersed nano-crystalline lithium titanate by using nanometer microreactor |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108134075A (en) * | 2017-12-07 | 2018-06-08 | 三峡大学 | A kind of sodium titanate microballoon and its application in sodium-ion battery |
CN108134075B (en) * | 2017-12-07 | 2020-04-24 | 三峡大学 | Sodium titanate microsphere and application thereof in sodium ion battery |
CN112467096A (en) * | 2020-10-30 | 2021-03-09 | 安普瑞斯(南京)有限公司 | Negative electrode material, preparation method thereof, electrode and secondary battery |
CN112467096B (en) * | 2020-10-30 | 2022-09-23 | 安普瑞斯(南京)有限公司 | Negative electrode material, preparation method thereof, electrode and secondary battery |
CN113193181A (en) * | 2021-04-23 | 2021-07-30 | 湖州杉杉新能源科技有限公司 | Pre-lithiated silica composite material, precursor, preparation method and application thereof |
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