CN104282883A - Composite anode material for lithium ion battery, negative plate of lithium ion battery and lithium ion battery - Google Patents
Composite anode material for lithium ion battery, negative plate of lithium ion battery and lithium ion battery Download PDFInfo
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- CN104282883A CN104282883A CN201410541098.1A CN201410541098A CN104282883A CN 104282883 A CN104282883 A CN 104282883A CN 201410541098 A CN201410541098 A CN 201410541098A CN 104282883 A CN104282883 A CN 104282883A
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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 provides a composite anode material for a lithium ion battery, a preparation method of the composite anode material, a negative plate of the lithium ion battery and the lithium ion battery. Lithium titanate/carbon doped composite microspheres with pore structures are arranged inside the composite anode material. The preparation method of the composite anode material comprises the following steps: performing ball-milling and mixing on a proper amount of acetate or oxalate in at least one of nickel, cerium and chromium, a lithium source and a titanium source, sintering in an inert atmosphere, thereby obtaining a lithium titanate base material doped with at least one metal element in carbon, nickel, chromium and cerium; mixing the base material, a soluble carbon-containing organic adhesive, a nitrogen-containing carbon material and a solvent to be uniform, thereby obtaining slurry; and performing spray drying on the slurry, carbonizing, thereby obtaining the composite anode material. The composite anode material has high conductivity, rate capability and cycling stability and high specific capacity; and the preparation method is simple in process, environmentally friendly, low in energy consumption and cost and easy for large-scale production. The invention also provides a negative plate of the lithium ion battery and the lithium ion battery which are prepared from the composite anode material.
Description
Technical field
This relates to composite negative electrode material of lithium ion battery and preparation method thereof, the anode plate for lithium ionic cell prepared by this composite negative pole material and lithium ion battery, belong to technical field of lithium ion, particularly relate to lithium ion battery negative material preparing technical field.
Background technology
There is the lithium titanate of spinel structure, in charge and discharge process, lithium ion insertion and deintercalation almost do not affect material structure, be called " zero strain " material, charge and discharge platform is good and platform capacity can reach more than 90% of discharge capacity, good cycle, well, preparation method is simple for security feature and cycle characteristics, cost is lower, has become the extremely wide lithium ion battery negative material of commercial applications prospect at present.
Lithium titanate not only has above-mentioned many outstanding advantages as lithium ion battery negative material, and the electrochemical diffusion coefficient of lithium ion is 2 × 10 at normal temperatures
-8cm
2/ s, an order of magnitude larger than Carbon anode.But its intrinsic conductivity is lower is only 10
-9s/cm, belongs to typical insulator, poorly conductive, thus when causing high power charging-discharging, poor-performing and special capacity fade are very fast, and heavy-current discharge performance is undesirable.The electric conductivity of material can be improved, to obtain good fast charging and discharging performance and cycle performance by doping.Chinese invention patent CA201210295308.4 " lithium titanate anode material of a kind of yttrium modification and preparation method thereof " adopts solid phase method to prepare a kind of lithium titanate anode material of yttrium modification, this negative material has good chemical property and higher coulombic efficiency, has high coulombic efficiency equally when the high magnification test of 10C.Chinese invention patent CN102637864A " lithium titanate anode material of a kind of lanthanum that adulterates and preparation method thereof " adopts solid phase method to prepare the lithium titanate anode material of La doped equally, by the Trace La refinement crystal grain that adulterates, improve the chemical property of lithium titanate.The mode of above-mentioned two kinds of single metal ions of doping achieves useful effect all to a certain extent.The Chinese invention patent CN102646810A preparation method of coated lithium titanate composite anode material " a kind of three-dimensional porous Graphene doping with " discloses a kind of three-dimensional porous Graphene and adulterate and the preparation method of coated lithium titanate composite material, is effectively improved the high magnification chemical property of lithium titanate anode material by doping carbon material.But the three-dimensional porous grapheme material described in this patent is by hydro thermal method process, and still effectively can not suppress the stacking and agglomeration perhaps in sintering process of the lamella of Graphene, this limits the performance of its performance to a certain extent.Document " Sol-hydrothermal synthesis of Li
4ti
5o
12/ rutile-TiO
2composite as high rate anode materialforlithiumionbatteries " (Ceramics International; 2014 (40): 13553 ~ 13558) report a kind of lithium titanate/rutile titanium dioxide combination electrode material adopting sol hydrothermal synthesis legal system standby; and the specific capacity of this combination electrode material when 1C multiplying power is 157.6 mAh/g; but; the preparation technology of the method is comparatively complicated, is not suitable for industrialization promotion.
Summary of the invention
For lithium titanate anode material poorly conductive, high rate performance is not high, cycle characteristics needs the above-mentioned shortcoming existed in the problem that improves further and preparation process, first the present invention adopts metallic element and carbon co-doped preparation lithium titanate matrix material, then the method combined by spraying dry and carbonization technique, in above-mentioned substrate material surface carbon coated, finally obtains lithium titanate composite anode material, the anode plate for lithium ionic cell prepared by this negative material and lithium ion battery.Technical scheme of the present invention is realized by following method and step:
The invention provides a kind of composite negative electrode material of lithium ion battery, this composite negative pole material is doped lithium titanate/carbon complex microsphere that inside has gap structure; Described complex microsphere is made up of the lithium titanate matrix material of at least one metallic element and the carbon coating layer two parts on surface in doping carbon and nickel, chromium, cerium;
Preferably, the molar content of described doped metallic elements is 0.1 ~ 5% of lithium titanate;
Preferably, described carbon coating layer is solubility carbon containing organic bond, nitrogenous material with carbon element and the product of solvent after carbonization, wherein, the molar content of carbon coating layer is 0.1 ~ 15% of lithium titanate, and the mass percentage of nitrogenous material with carbon element is 0.5 ~ 5% of carbon coating layer gross mass;
Preferably, described nitrogenous material with carbon element to collect the nitrogenous material with carbon element with sub-hole and microcellular structure obtained after the discarded cigarette filter come carries out nitrogen treatment 1.5 ~ 3h with the heating rate of 2 ~ 8 DEG C/min in ammonia atmosphere between 800 ~ 950 DEG C.
Present invention also offers the preparation method of composite negative electrode material of lithium ion battery, concrete preparation process is:
(1) carry out ball milling or three-dimensional hybrid after the acetate of at least one in appropriate nickel, cerium and chromium or oxalates, lithium source and titanium source being weighed according to certain element proportioning, after dry, cross 200 mesh sieves;
(2) product after sieving in step (1) is calcined 3 ~ 12h in the inert atmosphere of 550 ~ 850 DEG C, crush and screen after Temperature fall, obtain the lithium titanate matrix material of at least one metallic element in doping carbon and nickel, chromium, cerium;
(3) the lithium titanate matrix material in step (2), solubility carbon containing organic bond, nitrogenous material with carbon element and solvent Homogeneous phase mixing are obtained slurry, after slurry is spray-dried, carbonization, obtain composite negative electrode material of lithium ion battery;
Preferably, lithium source described in step (1) is at least one in lithium hydroxide and lithium acetate, described titanium source is the mixture of unformed ultra-fine metatitanic acid and titanium dioxide, wherein, 0 < (mol ratio)≤1 of unformed ultra-fine metatitanic acid and titanium dioxide;
Preferably, described ball milling comprise in planetary type ball-milling, blue formula ball milling or high-energy ball milling any one, Ball-milling Time is 1 ~ 15h, more preferably 2 ~ 10h, is more preferably 3 ~ 8h;
Preferably, ball-milling medium used is zirconia ball, and solvent is deionized water, or deionized water and absolute ethyl alcohol, polyvinyl alcohol, ethylene glycol, n-butanol, isobutanol, acetone, the mixture of at least one in cyclohexane.
Preferably, described three-dimensional hybrid adopts three-dimensional mixer, and incorporation time is 1 ~ 25h, more preferably 2 ~ 20h, is more preferably 3 ~ 15h;
Preferably, the inert atmosphere described in step (2) is at least one in high-purity argon gas and high pure nitrogen, and in described calcination process, heating rate is 1 ~ 10 DEG C/min;
Preferably, the solubility carbon containing organic bond described in step (3) is selected from the combination of any one or at least two kinds in glucose, monocrystal rock sugar, sucrose, starch, methylcellulose, ethyl cellulose, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, phenolic resins, vinyl pyrrolidone, epoxy resin, glycan alcohol, shitosan, furane resins, polymethyl methacrylate, Kynoar or polyvinyl chloride;
Preferably, solvent described in step (3) is the combination of any one or at least two kinds in deionized water, absolute ethyl alcohol, acetone, stupid, toluene, dimethyl formamide, the combination of any one or at least two kinds more preferably in deionized water, absolute ethyl alcohol and acetone;
Preferably, described in step (3), the temperature of carbonization treatment is preferably 500 ~ 900 DEG C, and the time is 0.5 ~ 20h;
Preferably, described in step (3), carbonization is carried out in protective atmosphere, and described protective atmosphere to be preferably in nitrogen, argon gas the combination of any one or at least two kinds.
The invention provides a kind of anode plate for lithium ionic cell, described anode plate for lithium ionic cell is made up of collector and the coating material such as composite negative electrode material of lithium ion battery, conductive agent, binding agent on a current collector, and described composite negative electrode material of lithium ion battery is the composite negative pole material described in claim arbitrary in above-mentioned preparation process;
Preferably, in described conductive agent, comprise the arbitrary nitrogenous material with carbon element described in above-mentioned preparation process, and the mass fraction of above-mentioned nitrogenous material with carbon element in conductive agent is 0.1 ~ 5%.
Further, in order to investigate the chemical property of Lithium-titanate composite negative pole, by the arbitrary lithium titanate composite anode material described in said method and step, uniform sizing material is mixed with by the mode of ultrasonic disperse and rapid stirring and 1-METHYLPYRROLIDONE after conductive agent containing nitrogenous material with carbon element and Kynoar weigh according to the mass ratio of 80:10:10, apply on a current collector after froth in vacuum, flatten on roll squeezer after 80 DEG C of dryings and make electrode diaphragm, this diaphragm is washed into the disk that diameter is 9mm, it is assembled into button cell with lithium sheet after 120 DEG C of vacuumize 12h, electrolyte adopts the LiPF containing 1mol/L
6ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).In the voltage range of 0.03 ~ 3.0V, charge-discharge test is carried out after this button cell is placed 24h.
The invention provides a kind of lithium ion battery, described lithium ion battery comprises composite cathode material for lithium ion cell in above-mentioned preparation process described in arbitrary step and anode plate for lithium ionic cell.
Outstanding advantages of the present invention and good effect as follows:
(1) the present invention adopts metallic element and carbon co-doped preparation lithium titanate matrix material, compared with other doping methods, adopt the negative material prepared of the method can effectively stop in charge and discharge process effectively to reduce lithium titanate and electrolyte reacts, thus effectively can improve the chemical property of composite negative pole material.
(2) the present invention is in the process of preparation lithium titanate composite anode material, on the basis adopting metallic element and carbon co-doped preparation lithium titanate matrix material, the method combined by spraying dry and carbonization technique is in above-mentioned substrate material surface carbon coated, final acquisition lithium titanate composite anode material, surface coated carbon-coating serves the effect of electric transmission resilient coating in negative material, the lithium ion diffusion coefficient of lithium titanate composite anode material can be increased, can effectively improve its cycle performance while raising conductivity and high rate performance.
Composite negative pole material provided by the invention has good conductivity and high rate performance, higher specific capacity and good cyclical stability, circulation coulombic efficiency is greater than 90% first, when current density is 120mA/g, the specific capacity after 80 times that circulates is greater than 242mAh/g, and the capability retention after 150 times that circulates when 10C multiplying power is greater than 95%.Present invention also offers the anode plate for lithium ionic cell and lithium ion battery prepared by above-mentioned composite negative pole material.Preparation method's technique provided by the invention is simple, environmentally friendly, energy consumption and with low cost, is easy to large-scale production.
Specific embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that following examples are only the preferred embodiments of the present invention, so that understand the present invention better, thus should not be considered as limiting scope of the present invention.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, and any amendment made, equivalent replacement or improvement etc., all should be included within protection scope of the present invention.
Embodiment 1
Weigh lithium acetate, nickel acetate, chromium acetate, ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, the element proportioning of Li and Ti meets chemical formula Li
4ti
5o
12the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 1, the molar content of nickel and chromium is 5% of lithium titanate, above-mentioned raw material are carried out in deionized water blue formula ball milling 1h, 200 mesh sieves are crossed after dry, then the product after sieving is calcined 12h in the argon gas of 550 DEG C, crush and screen after Temperature fall, obtain the lithium titanate matrix material of doping nickel, chromium and carbon.By this basis material, glucose, in ammonia, obtain slurry with the heating rate of 2 DEG C/min through the nitrogenous material with carbon element of 800 DEG C of nitrogen treatment 3h and deionized water Homogeneous phase mixing, wherein, the mass percentage of nitrogenous material with carbon element is 0.5% of carbon coating layer gross mass, slurry is spray-dried, then in argon gas in 900 DEG C of carbonization treatment 0.5h, obtain composite negative electrode material of lithium ion battery, wherein the mass percentage of this composite negative pole material material with carbon-coated surface layer is 0.1% of lithium titanate.
Uniform sizing material is mixed with by the mode of ultrasonic disperse and rapid stirring and 1-METHYLPYRROLIDONE after above-mentioned lithium titanate composite anode material after carbonization treatment, the conductive agent containing nitrogenous material with carbon element and Kynoar being weighed according to the mass ratio of 80:10:10, apply on a current collector after froth in vacuum, flatten on roll squeezer after 80 DEG C of dryings and make electrode diaphragm, this diaphragm is washed into the disk that diameter is 9mm, after 120 DEG C of vacuumize 12h, be assembled into button cell with lithium sheet, electrolyte adopts the LiPF containing 1mol/L
6ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).In the voltage range of 0.03 ~ 3.0V, charge-discharge test is carried out after this button cell is placed 24h, when current density is 120mA/g, circulation coulombic efficiency is 93% first, and the specific capacity after 80 times that circulates is 243 mAh/g, and the capability retention after 150 times that circulates when 10C multiplying power is 95.6%.
Embodiment 2
Weigh lithium acetate, nickel oxalate, cerium oxalate, ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, the element proportioning of Li and Ti meets chemical formula Li
4ti
5o
12the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 0.1, the molar content of nickel and cerium is 1% of lithium titanate, by above-mentioned raw material mixer mill 1h in three-dimensional mixer, cross the product after 200 mesh sieves and calcine 3h in the argon gas of 850 DEG C, crush and screen after Temperature fall, obtain the lithium titanate matrix material of doping nickel, cerium and carbon.By this basis material, ethyl cellulose, polyethylene glycol, in ammonia to obtain slurry with the heating rate of 8 DEG C/min through the nitrogenous material with carbon element of 950 DEG C of nitrogen treatment 1.5h and deionized water Homogeneous phase mixing, wherein, the mass percentage of nitrogenous material with carbon element is 5% of carbon coating layer gross mass, slurry is spray-dried, then in argon gas in 500 DEG C of carbonization treatment 20h, obtain composite negative electrode material of lithium ion battery, wherein the mass percentage of this composite negative pole material material with carbon-coated surface layer is 15% of lithium titanate.
Above-mentioned lithium titanate composite anode material after carbonization treatment is made into negative electricity pole piece and button cell, preparation method is with embodiment 1, in the voltage range of 0.03 ~ 3.0V, charge-discharge test is carried out after this button cell is placed 24h, when current density is 120mA/g, circulation coulombic efficiency is 94% first, the specific capacity after 80 times that circulates is 245 mAh/g, and the capability retention after 150 times that circulates when 10C multiplying power is 96.2%.
Embodiment 3
Weigh lithium hydroxide, nickel oxalate, ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, the element proportioning of Li and Ti meets chemical formula Li
4ti
5o
12the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 0.5, the molar content of nickel is 3% of lithium titanate, by above-mentioned raw material mixer mill 3h in three-dimensional mixer, cross the product after 200 mesh sieves and calcine 5h in the argon gas of 850 DEG C, crush and screen after Temperature fall, obtain the lithium titanate matrix material of doping nickel and carbon.By this basis material, shitosan, phenolic resins, in ammonia to obtain slurry with the heating rate of 5 DEG C/min through the nitrogenous material with carbon element of 900 DEG C of nitrogen treatment 2h and absolute ethyl alcohol Homogeneous phase mixing, wherein, the mass percentage of nitrogenous material with carbon element is 3% of carbon coating layer gross mass, slurry is spray-dried, then in nitrogen in 600 DEG C of carbonization treatment 10h, obtain composite negative electrode material of lithium ion battery, wherein the mass percentage of this composite negative pole material material with carbon-coated surface layer is 10% of lithium titanate.
Above-mentioned lithium titanate composite anode material after carbonization treatment is made into negative electricity pole piece and button cell, preparation method is with embodiment 1, in the voltage range of 0.03 ~ 3.0V, charge-discharge test is carried out after this button cell is placed 24h, when current density is 120mA/g, circulation coulombic efficiency is 94.3% first, the specific capacity after 80 times that circulates is 244.1 mAh/g, and the capability retention after 150 times that circulates when 10C multiplying power is 96.5%.
Embodiment 4
Weigh lithium acetate, chromium acetate, cerous acetate, ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, the element proportioning of Li and Ti meets chemical formula Li
4ti
5o
12the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 0.7, the molar content of chromium and cerium is 2% of lithium titanate, above-mentioned raw material are carried out high-energy ball milling 5h in the mixed liquor of deionized water and absolute ethyl alcohol, 200 mesh sieves are crossed after dry, then the product after sieving is calcined 8h in the mixed atmosphere of the nitrogen of 750 DEG C and argon gas, crush and screen after Temperature fall, obtain the lithium titanate matrix material of chromium-doped, cerium and carbon.By this basis material, starch, methylcellulose, in ammonia, obtain slurry with the heating rate of 4 DEG C/min through the nitrogenous material with carbon element of 850 DEG C of nitrogen treatment 2h and deionized water Homogeneous phase mixing, wherein, the mass percentage of nitrogenous material with carbon element is 1% of carbon coating layer gross mass, slurry is spray-dried, then in argon gas in 900 DEG C of carbonization treatment 1h, obtain composite negative electrode material of lithium ion battery, wherein the mass percentage of this composite negative pole material material with carbon-coated surface layer is 5% of lithium titanate.
Above-mentioned lithium titanate composite anode material after carbonization treatment is made into negative electricity pole piece and button cell, preparation method is with embodiment 1, in the voltage range of 0.03 ~ 3.0V, charge-discharge test is carried out after this button cell is placed 24h, when current density is 120mA/g, circulation coulombic efficiency is 96% first, the specific capacity after 80 times that circulates is 246.3 mAh/g, and the capability retention after 150 times that circulates when 10C multiplying power is 97.5%.
Claims (11)
1. composite negative electrode material of lithium ion battery, is characterized in that, described composite negative pole material is doped lithium titanate/carbon complex microsphere that inside has gap structure; Described complex microsphere is made up of the lithium titanate matrix material of at least one metallic element and the carbon coating layer two parts on surface in doping carbon and nickel, chromium, cerium.
2. composite negative electrode material of lithium ion battery as claimed in claim 1, it is characterized in that, the molar content of described doped metallic elements is 0.1 ~ 5% of lithium titanate.
3. composite negative electrode material of lithium ion battery as claimed in claim 1, it is characterized in that, described carbon coating layer is solubility carbon containing organic bond, nitrogenous material with carbon element and the product of solvent after carbonization, wherein, the mass percentage of carbon coating layer is 0.1 ~ 15% of lithium titanate gross mass, and the mass percentage of nitrogenous material with carbon element is 0.5 ~ 5% of carbon coating layer gross mass.
4. the preparation method of composite negative electrode material of lithium ion battery, is characterized in that, comprises the following steps:
(1) carry out ball milling or three-dimensional hybrid after the acetate of at least one in appropriate nickel, cerium and chromium or oxalates, lithium source and titanium source being weighed according to certain element proportioning, after dry, cross 200 mesh sieves;
(2) product after sieving in step (1) is calcined 3 ~ 12h in the inert atmosphere of 550 ~ 850 DEG C, crush and screen after Temperature fall, obtain the lithium titanate matrix material of at least one metallic element in doping carbon and nickel, chromium, cerium;
(3) the lithium titanate matrix material in step (2), solubility carbon containing organic bond, nitrogenous material with carbon element and solvent Homogeneous phase mixing are obtained slurry, after slurry is spray-dried, carbonization, obtain composite negative electrode material of lithium ion battery.
5. composite negative pole material according to claim 3, it is characterized in that, described nitrogenous material with carbon element to collect the nitrogenous material with carbon element with sub-hole and microcellular structure obtained after the discarded cigarette filter come carries out nitrogen treatment 1.5 ~ 3h with the heating rate of 2 ~ 8 DEG C/min in ammonia atmosphere between 800 ~ 950 DEG C.
6. according to the preparation method of the composite negative pole material described in claim 4, it is characterized in that, lithium source described in step (1) is at least one in lithium hydroxide and lithium acetate, described titanium source is the mixture of unformed ultra-fine metatitanic acid and titanium dioxide, wherein, 0 < (mol ratio)≤1 of unformed ultra-fine metatitanic acid and titanium dioxide.
7. according to the preparation method of the composite negative pole material described in claim 4, it is characterized in that, ball milling described in step (1) comprise in planetary type ball-milling, blue formula ball milling or high-energy ball milling any one, Ball-milling Time is 1 ~ 15h, more preferably 2 ~ 10h, is more preferably 3 ~ 8h;
Preferably, ball-milling medium used is zirconia ball, and solvent is deionized water, or deionized water and absolute ethyl alcohol, polyvinyl alcohol, ethylene glycol, n-butanol, isobutanol, acetone, the mixture of at least one in cyclohexane.
Further, described three-dimensional hybrid adopts three-dimensional mixer, and incorporation time is 1 ~ 25h, more preferably 2 ~ 20h, is more preferably 3 ~ 15h.
8. according to the preparation method of the composite negative pole material described in claim 4, it is characterized in that, inert atmosphere described in step (2) is at least one in high-purity argon gas and high pure nitrogen, and in described calcination process, heating rate is 1 ~ 10 DEG C/min.
9. according to the preparation method of the composite negative pole material described in claim 4, it is characterized in that, the solubility carbon containing organic bond described in step (3) is selected from the combination of any one or at least two kinds in glucose, monocrystal rock sugar, sucrose, starch, methylcellulose, ethyl cellulose, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, phenolic resins, vinyl pyrrolidone, epoxy resin, glycan alcohol, shitosan, furane resins, polymethyl methacrylate, Kynoar or polyvinyl chloride;
Preferably, solvent described in step (3) is the combination of any one or at least two kinds in deionized water, absolute ethyl alcohol, acetone, stupid, toluene, dimethyl formamide, the combination of any one or at least two kinds more preferably in deionized water, absolute ethyl alcohol and acetone;
Preferably, described in step (3), the temperature of carbonization treatment is preferably 500 ~ 900 DEG C, and the time is 0.5 ~ 20h;
Preferably, described in step (3), carbonization is carried out in protective atmosphere, and described protective atmosphere to be preferably in nitrogen, argon gas the combination of any one or at least two kinds.
10. anode plate for lithium ionic cell, it is characterized in that, described anode plate for lithium ionic cell is made up of collector and the coating material such as composite negative electrode material of lithium ion battery, conductive agent, binding agent on a current collector, the composite negative pole material of described composite negative electrode material of lithium ion battery as described in claim arbitrary in claim 1 ~ 9;
Preferably, in described conductive agent, comprise the nitrogenous material with carbon element as described in claim arbitrary in claim 3 ~ 5, and the mass fraction of above-mentioned nitrogenous material with carbon element in conductive agent is 0.1 ~ 5%.
11. lithium ion batteries, is characterized in that, described lithium ion battery comprises the anode plate for lithium ionic cell described in claim 10.
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| CN106158404A (en) * | 2016-08-12 | 2016-11-23 | 深圳博磊达新能源科技有限公司 | A kind of ternary oxide/conductive agent/carbon/polypyrrole combination electrode material, pole piece and ultracapacitor |
| CN108258223A (en) * | 2018-01-19 | 2018-07-06 | 安徽工业大学 | A kind of preparation method of the spherical N doping C coated metal oxide negative materials of multilevel hierarchy |
| CN112310365A (en) * | 2020-06-28 | 2021-02-02 | 深圳市海洋王照明工程有限公司 | Composition, preparation method and application of composition in field of electrode materials |
| CN113594437A (en) * | 2021-07-21 | 2021-11-02 | 安徽天时新能源科技有限公司 | Negative active material of low-temperature lithium battery and preparation method thereof |
| CN116081682A (en) * | 2023-01-30 | 2023-05-09 | 湖北钛时代新能源有限公司 | Preparation method and application of lithium titanate material |
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| GB202008880D0 (en) * | 2020-06-11 | 2020-07-29 | Johnson Matthey Plc | Process for manufacturing doped lithium titanate |
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| CN101000960A (en) * | 2006-12-29 | 2007-07-18 | 深圳市贝特瑞电子材料有限公司 | Composite lithium titanate electrode material and preparation method thereof |
| CN101593830A (en) * | 2009-07-03 | 2009-12-02 | 郑州大学 | The preparation method of lithium ionic cell cathode material spinelle lithium titanate |
| WO2012153561A1 (en) * | 2011-05-12 | 2012-11-15 | 宇部興産株式会社 | Lithium titanate particles, active material, and method for producing lithium titanate particles |
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| CN106158404A (en) * | 2016-08-12 | 2016-11-23 | 深圳博磊达新能源科技有限公司 | A kind of ternary oxide/conductive agent/carbon/polypyrrole combination electrode material, pole piece and ultracapacitor |
| CN106158404B (en) * | 2016-08-12 | 2018-02-16 | 深圳博磊达新能源科技有限公司 | A kind of ternary oxide/conductive agent/carbon/polypyrrole combination electrode material, pole piece and ultracapacitor |
| CN108258223A (en) * | 2018-01-19 | 2018-07-06 | 安徽工业大学 | A kind of preparation method of the spherical N doping C coated metal oxide negative materials of multilevel hierarchy |
| CN108258223B (en) * | 2018-01-19 | 2020-05-05 | 安徽工业大学 | Preparation method of spherical N-doped C-coated metal oxide negative electrode material with multilevel structure |
| CN112310365A (en) * | 2020-06-28 | 2021-02-02 | 深圳市海洋王照明工程有限公司 | Composition, preparation method and application of composition in field of electrode materials |
| CN113594437A (en) * | 2021-07-21 | 2021-11-02 | 安徽天时新能源科技有限公司 | Negative active material of low-temperature lithium battery and preparation method thereof |
| CN116081682A (en) * | 2023-01-30 | 2023-05-09 | 湖北钛时代新能源有限公司 | Preparation method and application of lithium titanate material |
| CN116081682B (en) * | 2023-01-30 | 2024-01-19 | 湖北钛时代新能源有限公司 | Preparation method and application of lithium titanate material |
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