CN104282883B - Composite negative electrode material of lithium ion battery and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery - Google Patents
Composite negative electrode material of lithium ion battery and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery Download PDFInfo
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- CN104282883B CN104282883B CN201410541098.1A CN201410541098A CN104282883B CN 104282883 B CN104282883 B CN 104282883B CN 201410541098 A CN201410541098 A CN 201410541098A CN 104282883 B CN104282883 B CN 104282883B
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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 kind of composite negative electrode material of lithium ion battery and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery, there is inside it doped lithium titanate/carbon complex microsphere of gap structure.His preparation method is by the lithium titanate matrix material of at least one metallic element during sintering obtains doping carbon and nickel, chromium, cerium in an inert atmosphere after at least one acetate in appropriate nickel, cerium and chromium or oxalates, lithium source and the mixing of titanium source ball milling, then this matrix material, solubility carbon containing organic bond, nitrogenous material with carbon element and solvent are uniformly mixed to get slurry, after slurry is spray-dried, carbonization, obtain composite negative pole material.This composite negative pole material has good electric conductivity, high rate performance and cyclical stability, higher specific capacity；Its preparation method technique is simple, and environmentally friendly, energy consumption is with low cost, it is easy to large-scale production.Present invention also offers the anode plate for lithium ionic cell and lithium ion battery prepared by above-mentioned composite negative pole material.
Description
Technical field
This relates to composite negative electrode material of lithium ion battery and preparation method thereof, the lithium prepared by this composite negative pole material
Ion battery negative plate and lithium ion battery, belong to technical field of lithium ion, particularly relates to lithium ion battery negative material
Material preparing technical field.
Background technology
Having the lithium titanate of spinel structure, in charge and discharge process, lithium ion inserts and material structure is not almost had by deintercalation
Having an impact, be referred to as " zero strain " material, charge and discharge platform is good and platform capacity is up to more than the 90% of discharge capacity, cyclicity
Can be good, security feature and cycle characteristics are good, and preparation method is simple, and cost is relatively low, has the most become commercial applications prospect pole
Its wide lithium ion battery negative material.
Lithium titanate not only has above-mentioned many outstanding advantages as lithium ion battery negative material, and, lithium at normal temperatures
The electrochemical diffusion coefficient of ion is 2 × 10-8cm2/ s, more order of magnitude greater than Carbon anode.But, its intrinsic conductivity is relatively low only
It is 10-9 S/cm, belongs to typical insulator, poorly conductive, thus when causing high power charging-discharging, poor-performing and specific capacity declines
Subtracting very fast, heavy-current discharge performance is undesirable.The electric conductivity of material can be improved by doping, preferably quickly fill to obtain
Discharge performance and cycle performance.Chinese invention patent CA201210295308.4 " lithium titanate anode material that a kind of yttrium is modified and
Its preparation method " use solid phase method to be prepared for the lithium titanate anode material that a kind of yttrium is modified, this negative material has good electricity
Chemical property and higher coulombic efficiency, have high coulombic efficiency equally when the high magnification of 10C is tested.Chinese invention patent
CN102637864A " lithium titanate anode material of a kind of lanthanum that adulterates and preparation method thereof " employing solid phase method equally is prepared for lanthanum and mixes
Miscellaneous lithium titanate anode material, has refined crystal grain by doping Trace La, has improve the chemical property of lithium titanate.Above two
The mode of single metal ion of adulterating achieves beneficial effect the most to a certain extent.Chinese invention patent CN102646810A
" doping of a kind of three-dimensional porous Graphene and the preparation method of cladding lithium titanate composite anode material " discloses a kind of three-dimensional porous
Graphene doping and the preparation method of cladding lithium titanate composite material, effectively improve lithium titanate anode material by doping material with carbon element
The high magnification chemical property of material.But, the three-dimensional porous grapheme material described in this patent is processed by hydro-thermal method,
Still can not effectively suppress lamella stacking and the perhaps agglomeration in sintering process of Graphene, this limits to a certain extent
Make the performance of its performance.Document " Sol-hydrothermal synthesis of Li4Ti5O12/rutile-TiO2
composite as high rate anode materialforlithiumionbatteries”(Ceramics
International, 2014 (40): 13553 ~ 13558) report a kind of metatitanic acid using sol hydrothermal synthesis method to prepare
Lithium/rutile titanium dioxide combination electrode material, this combination electrode material specific capacity when 1C multiplying power is 157.6 mAh/
G, but, the preparation technology of the method is complex, is not suitable for industrialization promotion.
Summary of the invention
For lithium titanate anode material poorly conductive, high rate performance is the highest, and cycle characteristics needs the problem improved further
And disadvantages mentioned above present in preparation process, the present invention is initially with metallic element and carbon co-doped preparation lithium titanate matrix material
Material, then by being spray-dried and the method that combines of carbonization technique is in above-mentioned substrate material surface carbon coated, finally obtains titanium
Acid lithium composite negative pole material, this negative material anode plate for lithium ionic cell prepared and lithium ion battery.The skill of the present invention
Art scheme is realized by following method and steps:
The invention provides a kind of composite negative electrode material of lithium ion battery, this composite negative pole material is that inside has space
The doped lithium titanate of structure/carbon complex microsphere；Described complex microsphere is by least one metallic element in adulterate carbon and nickel, chromium, cerium
Lithium titanate matrix material and surface carbon coating layer two parts composition；
Preferably, the molar content of described doped metallic elements is the 0.1 ~ 5% of lithium titanate；
Preferably, described carbon coating layer is that solubility carbon containing organic bond, nitrogenous material with carbon element and solvent are after carbonization
Product, wherein, the molar content of carbon coating layer is the 0.1 ~ 15% of lithium titanate, the weight/mass percentage composition of nitrogenous material with carbon element
For carbon coating layer gross mass 0.5 ~ 5%；
Preferably, described nitrogenous material with carbon element is will to collect the discarded cigarette filter come in ammonia atmosphere with 2～8
DEG C/min heating rate between 800～950 DEG C, carry out nitrogen treatment 1.5～3h after have sub-hole and the micropore that obtain tie
The nitrogenous material with carbon element of structure.
Present invention also offers the preparation method of composite negative electrode material of lithium ion battery, concrete preparation process is:
(1) by least one acetate in appropriate nickel, cerium and chromium or oxalates, lithium source and titanium source according to certain unit
Element proportioning carries out ball milling or three-dimensional hybrid, dried mistake 200 mesh sieve after weighing；
(2) product after sieving in step (1) calcines 3 ~ 12h, Temperature fall in the inert atmosphere of 550 ~ 850 DEG C
After crush and screen, it is thus achieved that the lithium titanate matrix material of at least one metallic element in doping carbon and nickel, chromium, cerium；
(3) by the lithium titanate matrix material in step (2), solubility carbon containing organic bond, nitrogenous material with carbon element and solvent
Uniformly it is mixed to get slurry, after slurry is spray-dried, carbonization, obtains composite negative electrode material of lithium ion battery；
Preferably, the lithium source described in step (1) is at least one in Lithium hydrate and Quilonorm (SKB), and described titanium source is
Unformed ultra-fine metatitanic acid and the mixture of titanium dioxide, wherein, 0 ＜ (unformed ultra-fine metatitanic acid and titanium dioxide mole
Than) 1；
Preferably, described ball milling includes any one in planetary type ball-milling, blue formula ball milling or high-energy ball milling, during ball milling
Between be 1～15h, more preferably 2～10h, more preferably 3～8h；
Preferably, ball-milling medium used is zirconia ball, and solvent is deionized water, or deionized water and anhydrous second
The mixture of at least one in alcohol, polyvinyl alcohol, ethylene glycol, n-butyl alcohol, isobutanol, acetone, hexamethylene.
Preferably, described three-dimensional hybrid use three-dimensional mixer, incorporation time is 1～25h, more preferably 2～
20h, 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, described
In calcination process, heating rate is 1 ~ 10 DEG C/min；
Preferably, the solubility carbon containing organic bond described in step (3) is selected from glucose, monocrystal rock sugar, sucrose, shallow lake
Powder, methylcellulose, ethyl cellulose, polyvinyl alcohol, Polyethylene Glycol, polyacrylonitrile, phenolic resin, vinyl pyrrolidone,
Any in epoxy resin, polysaccharide alcohol, chitosan, furane resins, polymethyl methacrylate, Kynoar or polrvinyl chloride
A kind of or the combination of at least two；
Preferably, solvent described in step (3) is deionized water, dehydrated alcohol, acetone, stupid, toluene, dimethylformamide
In any one or the combination of at least two, more preferably any one in deionized water, dehydrated alcohol and acetone
Or the combination of at least two；
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 is preferably nitrogen
Any one or the combination of at least two in gas, argon.
The present invention provides a kind of anode plate for lithium ionic cell, and described anode plate for lithium ionic cell is by collector and is coated on collection
The material compositions such as composite negative electrode material of lithium ion battery on fluid, conductive agent, binding agent, described lithium ion battery is with compound
Negative material is the composite negative pole material in above-mentioned preparation process described in any claim；
Preferably, described conductive agent comprises the arbitrary nitrogenous material with carbon element described in above-mentioned preparation process, and above-mentioned contain
Nitrogen material with carbon element mass fraction in conductive agent is 0.1 ~ 5%.
Further, in order to investigate the chemical property of Lithium-titanate composite negative pole, by said method and step
Described arbitrary lithium titanate composite anode material, the conductive agent containing nitrogenous material with carbon element and Kynoar are according to 80:10:10's
Mass ratio is configured to uniform sizing material, through vacuum with N-Methyl pyrrolidone after weighing by the way of ultrasonic disperse and quick stirring
Coating on a current collector after de-bubble, 80 DEG C of dried pressings on roll squeezer make electrode diaphragm, are washed into a diameter of by this diaphragm
The disk of 9mm, is assembled into button cell with lithium sheet by it after 120 DEG C of vacuum drying 12h, and electrolyte uses containing 1mol/L's
LiPF6Ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).This button cell is placed after 24h 0.03 ~
Charge-discharge test is carried out in the voltage range of 3.0V.
The present invention provides a kind of lithium ion battery, and described lithium ion battery comprises in above-mentioned preparation process described in either step
Composite cathode material for lithium ion cell and anode plate for lithium ionic cell.
Outstanding advantages and the good effect of the present invention are as follows:
(1) present invention uses metallic element and carbon co-doped preparation lithium titanate matrix material, with other doping method phases
Ratio, the negative material using the method to prepare can effectively stop can effectively reduce lithium titanate and electrolyte generation in charge and discharge process
Reaction, it is thus possible to be effectively improved the chemical property of composite negative pole material.
(2) present invention is during preparation lithium titanate composite anode material, is using metallic element and carbon co-doped system
On the basis of standby lithium titanate matrix material, by being spray-dried the method combined with carbonization technique at above-mentioned substrate material surface
Carbon coated, finally obtains lithium titanate composite anode material, and surface coated carbon-coating serves electric transmission in negative material and delays
Rush the effect of layer, the lithium ion diffusion coefficient of lithium titanate composite anode material can be increased, improve electric conductivity and high rate performance
Its cycle performance can be effectively improved simultaneously.
The composite negative pole material that the present invention provides has good electric conductivity and high rate performance, higher specific capacity and very well
Cyclical stability, circulation coulombic efficiency is more than 90% first, and when electric current density is 120mA/g, after circulating 80 times, specific capacity is more than
242mAh/g, after circulating 150 times when 10C multiplying power, capability retention is more than 95%.Present invention also offers by above-mentioned composite negative pole
Anode plate for lithium ionic cell prepared by material and lithium ion battery.The preparation method technique that the present invention provides is simple, to environment friend
Good, energy consumption is with low cost, it is easy to large-scale production.
Specific embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.Those skilled in the art will manage
Solving, following example are only the preferred embodiments of the present invention, in order to be more fully understood that the present invention, thus should not be regarded as limiting this
The scope of invention.For a person skilled in the art, the present invention can have various modifications and variations, all essences in the present invention
Within god and principle, any amendment, equivalent or the improvement etc. made, should be included within the scope of the present invention.
Embodiment 1
Weigh Quilonorm (SKB), nickel acetate, chromium acetate, ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, Li and
The element proportioning of Ti meets chemical formula Li4Ti5O12, the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 1, moles the hundred of nickel and chromium
Point content is the 5% of lithium titanate, and above-mentioned raw material carries out blue formula ball milling 1h in deionized water, dried mistake 200 mesh sieve, so
After will sieve after product in the argon of 550 DEG C, calcine 12h, crush and screen after Temperature fall, it is thus achieved that doping nickel, chromium and carbon
Lithium titanate matrix material.By this matrix material, glucose, in ammonia with the heating rate of 2 DEG C/min at 800 DEG C of nitridations
Nitrogenous material with carbon element and the deionized water of reason 3h are uniformly mixed to get slurry, and wherein, the weight/mass percentage composition of nitrogenous material with carbon element is carbon
The 0.5% of clad gross mass, slurry is spray-dried, then in 900 DEG C of carbonization treatment 0.5h in argon, it is thus achieved that lithium from
Sub-battery composite negative pole material, wherein the weight/mass percentage composition of this composite negative pole material material with carbon-coated surface layer is lithium titanate
0.1%。
By above-mentioned lithium titanate composite anode material after carbonization treatment, the conductive agent containing nitrogenous material with carbon element and poly-inclined fluorine
Ethylene is joined with N-Methyl pyrrolidone after weighing according to the mass ratio of 80:10:10 by the way of ultrasonic disperse and quick stirring
Making uniform sizing material, coat on a current collector after froth in vacuum, 80 DEG C of dried pressings on roll squeezer make electrode diaphragm,
This diaphragm being washed into the disk of a diameter of 9mm, is assembled into button cell with lithium sheet after 120 DEG C of vacuum drying 12h, electrolyte is adopted
With the LiPF containing 1mol/L6Ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).This button cell is placed
In the voltage range of 0.03 ~ 3.0V, charge-discharge test is carried out after 24h, when electric current density is 120mA/g, circulation coulomb effect first
Rate is 93%, and after circulating 80 times, specific capacity is 243 mAh/g, and after circulating 150 times when 10C multiplying power, capability retention is 95.6%.
Embodiment 2
Weigh Quilonorm (SKB), nickel oxalate, Sedemesis., ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, Li and
The element proportioning of Ti meets chemical formula Li4Ti5O12, the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 0.1, nickel and cerium mole
Percentage composition is the 1% of lithium titanate, by above-mentioned raw material mixer mill 1h in three-dimensional mixer, crosses the product after 200 mesh sieves and exists
The argon of 850 DEG C is calcined 3h, crushes and screens after Temperature fall, it is thus achieved that doping nickel, cerium and the lithium titanate matrix material of carbon.Should
Matrix material, ethyl cellulose, Polyethylene Glycol, in ammonia with the heating rate with 8 DEG C/min through 950 DEG C of nitrogen treatment
The nitrogenous material with carbon element of 1.5h and deionized water are uniformly mixed to get slurry, and wherein, the weight/mass percentage composition of nitrogenous material with carbon element is carbon
The 5% of clad gross mass, slurry is spray-dried, then in 500 DEG C of carbonization treatment 20h in argon, it is thus achieved that lithium-ion electric
Pond composite negative pole material, wherein weight/mass percentage composition is lithium titanate the 15% of this composite negative pole material material with carbon-coated surface layer.
Above-mentioned lithium titanate composite anode material after carbonization treatment is fabricated to negative electricity pole piece and button cell, preparation
Method, with embodiment 1, carries out charge-discharge test, electric current after this button cell is placed 24h in the voltage range of 0.03 ~ 3.0V
When density is 120mA/g, circulation coulombic efficiency is 94% first, and after circulating 80 times, specific capacity is 245 mAh/g, when 10C multiplying power
After circulating 150 times, capability retention is 96.2%.
Embodiment 3
Lithium hydrate, nickel oxalate, ultra-fine metatitanic acid and titanium dioxide, wherein, Li's and Ti is weighed according to certain proportioning
Element proportioning meets chemical formula Li4Ti5O12, the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 0.5, the molar content of nickel
For the 3% of lithium titanate, by above-mentioned raw material mixer mill 3h in three-dimensional mixer, cross the argon that the product after 200 mesh sieves is at 850 DEG C
Gas is calcined 5h, crushes and screens after Temperature fall, it is thus achieved that doping nickel and the lithium titanate matrix material of carbon.By this matrix material, shell
Polysaccharide, phenolic resin, in ammonia 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 nothing
Water-ethanol is uniformly mixed to get slurry, and wherein, the weight/mass percentage composition of nitrogenous material with carbon element is the 3% of carbon coating layer gross mass, will slurry
Expect spray-dried, then in 600 DEG C of carbonization treatment 10h in nitrogen, it is thus achieved that composite negative electrode material of lithium ion battery, wherein
Weight/mass percentage composition is lithium titanate the 10% of this composite negative pole material material with carbon-coated surface layer.
Above-mentioned lithium titanate composite anode material after carbonization treatment is fabricated to negative electricity pole piece and button cell, preparation
Method, with embodiment 1, carries out charge-discharge test, electric current after this button cell is placed 24h in the voltage range of 0.03 ~ 3.0V
When density is 120mA/g, circulation coulombic efficiency is 94.3% first, and after circulating 80 times, specific capacity is 244.1 mAh/g, at 10C times
After circulating 150 times during rate, capability retention is 96.5%.
Embodiment 4
Weigh Quilonorm (SKB), chromium acetate, Cerium triacetate, ultra-fine metatitanic acid and titanium dioxide according to certain proportioning, wherein, Li and
The element proportioning of Ti meets chemical formula Li4Ti5O12, the mol ratio of ultra-fine metatitanic acid and titanium dioxide is 0.7, chromium and cerium mole
Percentage composition is the 2% of lithium titanate, and above-mentioned raw material carries out in the mixed liquor of deionized water and dehydrated alcohol high-energy ball milling
5h, dried mistake 200 mesh sieve, the product after then sieving calcines 8h, certainly in the nitrogen of 750 DEG C and the mixed atmosphere of argon
So crush and screen after cooling, it is thus achieved that the lithium titanate matrix material of chromium-doped, cerium and carbon.By this matrix material, starch, Methyl cellulose
Element, in ammonia, heating rate with 4 DEG C/min uniformly mixes through nitrogenous material with carbon element and the deionized water of 850 DEG C of nitrogen treatment 2h
Conjunction obtains slurry, and wherein, the weight/mass percentage composition of nitrogenous material with carbon element is the 1% of carbon coating layer gross mass, by slurry through spray dried
Dry, then in 900 DEG C of carbonization treatment 1h in argon, it is thus achieved that composite negative electrode material of lithium ion battery, wherein this composite negative pole
The weight/mass percentage composition of material surface carbon coating layer is the 5% of lithium titanate.
Above-mentioned lithium titanate composite anode material after carbonization treatment is fabricated to negative electricity pole piece and button cell, preparation
Method, with embodiment 1, carries out charge-discharge test, electric current after this button cell is placed 24h in the voltage range of 0.03 ~ 3.0V
When density is 120mA/g, circulation coulombic efficiency is 96% first, and after circulating 80 times, specific capacity is 246.3 mAh/g, in 10C multiplying power
After Shi Xunhuan 150 times, capability retention is 97.5%.
Claims (7)
1. the preparation method of composite negative electrode material of lithium ion battery, described composite negative pole material is that inside has gap structure
Doped lithium titanate/carbon complex microsphere；Described complex microsphere is by the metatitanic acid of at least one metallic element in adulterate carbon and nickel, chromium, cerium
Carbon coating layer two parts composition on lithium matrix material and surface；The molar content of described doped metallic elements is metatitanic acid
The 0.1～5% of lithium；Described carbon coating layer is that solubility carbon containing organic bond, nitrogenous material with carbon element and solvent are after carbonization
Product, wherein, the weight/mass percentage composition of carbon coating layer is the 0.1～15% of lithium titanate gross mass, the quality hundred of nitrogenous material with carbon element
Dividing content is the 0.5～5% of carbon coating layer gross mass, it is characterised in that comprise the following steps:
(1) by least one acetate in appropriate nickel, cerium and chromium or oxalates, lithium source and titanium source according to certain element proportioning
Ball milling or three-dimensional hybrid, dried mistake 200 mesh sieve is carried out after weighing；
(2) product after sieving in step (1) calcines 3～12h in the inert atmosphere of 550～850 DEG C, powder after Temperature fall
Broken screening, it is thus achieved that the lithium titanate matrix material of at least one metallic element in adulterate carbon and nickel, chromium, cerium；
(3) by uniform with solvent to the lithium titanate matrix material in step (2), solubility carbon containing organic bond, nitrogenous material with carbon element
It is mixed to get slurry, after slurry is spray-dried, carbonization, obtains composite negative electrode material of lithium ion battery；
Described nitrogenous material with carbon element is will to collect the discarded cigarette filter come in ammonia atmosphere with the liter of 2～8 DEG C/min
The nitrogenous carbon material with sub-hole and microcellular structure that temperature speed obtains after carrying out nitrogen treatment 1.5～3h between 800～950 DEG C
Material.
The preparation method of composite negative pole material the most according to claim 1, it is characterised in that the lithium described in step (1)
Source is at least one in Lithium hydrate and Quilonorm (SKB), and described titanium source is unformed ultra-fine metatitanic acid and the mixing of titanium dioxide
Thing, wherein, the 0 unformed ultra-fine metatitanic acid of ＜ and the mol ratio 1 of titanium dioxide.
The preparation method of composite negative pole material the most according to claim 1, it is characterised in that the ball described in step (1)
Mill includes any one in planetary type ball-milling, blue formula ball milling or high-energy ball milling, and Ball-milling Time is 1～15h；Ball-milling medium is
Zirconia ball, solvent is deionized water, or deionized water and dehydrated alcohol, polyvinyl alcohol, ethylene glycol, n-butyl alcohol, isobutanol,
The mixture of at least one in acetone, hexamethylene；Described three-dimensional hybrid uses three-dimensional mixer, and incorporation time is 1～25h.
The preparation method of composite negative pole material the most according to claim 1, it is characterised in that lazy described in step (2)
Property atmosphere 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/minute
Clock.
The preparation method of composite negative pole material the most according to claim 1, it is characterised in that described in step (3) can
Dissolubility carbon containing organic bond is selected from glucose, monocrystal rock sugar, sucrose, starch, methylcellulose, ethyl cellulose, polyethylene
Alcohol, Polyethylene Glycol, polyacrylonitrile, phenolic resin, vinyl pyrrolidone, epoxy resin, polysaccharide alcohol, chitosan, furane resins,
Any one or the combination of at least two in polymethyl methacrylate, Kynoar or polrvinyl chloride；
Solvent described in step (3) is any one in deionized water, dehydrated alcohol, acetone, benzene, toluene, dimethylformamide
Plant or the combination of at least two；Described in step (3), the temperature of carbonization is 500～900 DEG C, and the time is 0.5～20h；
Described in step (3), carbonization is carried out in protective atmosphere.
6. anode plate for lithium ionic cell, it is characterised in that described anode plate for lithium ionic cell is by collector and is coated on collector
On composite negative electrode material of lithium ion battery, conductive agent, adhesive substance composition, described lithium ion battery composite negative pole material
Expect for the composite negative pole material as described in any claim in Claims 1 to 5.
7. lithium ion battery, it is characterised in that described lithium ion battery comprises the lithium ion battery negative described in claim 6
Sheet.
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| 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 |
| 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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