CN107482205A - A kind of graphite negative material of lithium ion battery and preparation method thereof - Google Patents
A kind of graphite negative material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN107482205A CN107482205A CN201710733239.3A CN201710733239A CN107482205A CN 107482205 A CN107482205 A CN 107482205A CN 201710733239 A CN201710733239 A CN 201710733239A CN 107482205 A CN107482205 A CN 107482205A
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- lithium ion
- ion battery
- negative material
- preparation
- graphite negative
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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 belongs to lithium ion battery material technical field, discloses a kind of graphite negative material of lithium ion battery and preparation method thereof.The preparation method is：Delanium is added after ammoniacal liquor is well mixed with absolute ethyl alcohol, ultrasonic disperse is uniform；Gained dispersion liquid is warming up to 40~50 DEG C, titanate esters are then added dropwise, heating stirring reacts 12~24h；Gained reaction solution is cooled to room temperature, centrifuges, and in 400~500 DEG C of 2~4h of heat preservation sintering after solid product drying, obtains the graphite negative material of lithium ion battery.The negative material of the present invention can be obviously improved the charge-discharge performance and cycle performance of lithium ion battery by the modification of titanium dioxide；Meanwhile Delanium is coated, the suitability of its negative material and electrolyte more preferably, can increase the cycle performance of battery.
Description
Technical field
The invention belongs to lithium ion battery material technical field, and in particular to a kind of graphite negative material of lithium ion battery and
Its preparation method.
Background technology
At present, the commonly used lithium ion battery negative material of in the market is mainly graphite-carbon negative pole material, is divided into graphite
Several forms such as class, hard carbon class and soft carbon class material, wherein graphite type material is one of focus of Study on Li-ion batteries.Due to
The interlamellar spacing of graphite is complete compared with little crystallization, and the quick deintercalation of lithium ion is on the one hand influenceed during lithium ion deintercalation, causes lithium
Diffusion velocity of the ion in graphite is slower, limits lithium ion battery high current charge-discharge ability；On the other hand, lithium ion takes off
The embedding volumetric expansion and contraction that can cause graphite 10% or so, ultimately result in layer structure destruction；Meanwhile the meeting in cyclic process
There is electrolyte solvent to be embedded in graphite layers altogether, due to the reduction of organic solvent, gas expansion can be produced under high current, causes stone
Ink sheet layer peels off, and causes active material loss and solid electrolyte interface (SEI) film to destroy, so as to cause cycle life to reduce.
For a long time, the capacitance for improving Delanium, the irreversible capacity loss first for reducing native graphite improve it
Cycle performance is always the emphasis researched and developed.Various producers have been developed for artificial plumbago negative pole material
Method, these methods are mostly that process route is longer from material asphalt, and production cost is higher.
Japan Patent JP10294111 carries out low temperature cladding to graphite Carbon Materials with pitch, must not be melted place after cladding
Reason and Light comminution, this method, which is difficult to, is evenly coated and keeps shape.Japan Patent
JP11246209 is to impregnate in pitch or tar graphite and hard charcoal particle at a temperature of 10~300 DEG C, then
Solvent separation and heat treatment are carried out, this method is difficult to be formed with certain thickness high polymeric in graphite and hard charcoal surface
Bitumen layer, the raising for graphite-structure stability are limited.Japan Patent
JP2000357506, hydrocarbon and its mixture are come to charcoal or graphite powder cladding cracking graphite, cracking graphite.Japan
Patent JP2000243398 is that graphite material is surface-treated using atmosphere caused by asphalt pyrolysis, and this method less may be used
The form of material of making to be modified is greatly improved, thus is restricted the raising of electrical property.Japan Patent
JP2002042816 is coated with CVD as raw material using aromatic hydrocarbons or coated with pitch phenolic resin, this with
JP2000182617 and JP2000283398 have similarity in effect.Japan Patent JP2000182617 is to use natural stone
Ink etc. and pitch or resin or its mixture Co carbonization, this method can reduce graphite material specific surface area, but be imitated in cladding
It is difficult to reach preferable control on fruit.Japan Patent JP2003100292, graphite is mixed with pitch, at a temperature of 600~800 DEG C
It is heat-treated.And JP200397357 is to mix graphite with heavy oil, then carry out delayed coking and heat treatment.Both the above is done
Method will typically have a pulverising step, can influence covered effect to a certain extent.
The content of the invention
For existing for above prior art in place of shortcoming and defect, primary and foremost purpose of the invention be to provide a kind of lithium from
The preparation method of sub- battery graphite cathode material.This method is coated on Delanium using metatitanic acid lipid, in artificial stone
Black surface forms titanium dioxide decorative layer.
Another object of the present invention is to provide a kind of graphite negative electrode of lithium ion battery being prepared by the above method
Material.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of graphite negative material of lithium ion battery, including following preparation process：
(1) Delanium is added after ammoniacal liquor is well mixed with absolute ethyl alcohol, ultrasonic disperse is uniform；
(2) dispersion liquid obtained by step (1) is warming up to 40~50 DEG C, then dropwise addition metatitanic acid fat, heating stirring reaction 12~
24h；
(3) reaction solution of step (2) is cooled to room temperature, centrifuged, at 400~500 DEG C after solid product drying
2~4h of heat preservation sintering, obtain the graphite negative material of lithium ion battery.
Preferably, the mass concentration of ammoniacal liquor described in step (1) is 36%~38%.
Preferably, the mass concentration of absolute ethyl alcohol described in step (1) is 99.8%.
Preferably, the metatitanic acid fat in step (2) and the weight ratio that Delanium in step (1) adds are 5~20:100；More
Preferably, the metatitanic acid fat and the weight ratio that Delanium adds are 5:100.
Preferably, the metatitanic acid fat refers to tetraisopropyl titanate, butyl titanate or tetraethyl titanate.
A kind of graphite negative material of lithium ion battery, is prepared by the above method.
The present invention preparation method and resulting product has the following advantages that and beneficial effect：
(1) after the present invention is by metatitanic acid fat cladding and sintering processes, one layer of amorphous titanium dioxide is formd in graphite surface
Titanium decorative layer, the increase of graphite average grain diameter, obtain a kind of amorphous titania modification graphite cathode material with core shell structure
Material.
(2) the titanium dioxide decorative layer of present invention gained negative material can provide graphite faster removal lithium embedded passage, and
And the modification of titanium dioxide can improve the embedding lithium platform of graphite.
(3) negative material of the invention can be obviously improved by the modification of titanium dioxide lithium ion battery charge and discharge it is electrical
Energy and cycle performance；Meanwhile Delanium is coated, the suitability of its negative material and electrolyte more preferably, can increase
The cycle performance of battery.
Brief description of the drawings
Fig. 1 is the electron microscope of the gained graphite negative material of lithium ion battery of embodiment 2.
Fig. 2 is (the C@TiO of the embodiment of the present invention 12And (the C@TiO of embodiment 2 0.15)20.05) gained cell negative electrode material and
Unmodified Delanium (C) prepares the cycle performance figure of lithium ion battery.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) Delanium is added after ammoniacal liquor is well mixed with absolute ethyl alcohol, ultrasonic disperse is uniform；
(2) dispersion liquid obtained by step (1) is warming up to 40 DEG C, is then added dropwise butyl titanate, butyl titanate and artificial
The weight ratio of graphite is 15:100, heating stirring reaction 20h；
(3) reaction solution of step (2) is cooled to room temperature, centrifuged, solid product is placed in horse after drying in oven
Not in stove, in 500 DEG C of heat preservation sintering 2h, the graphite negative material of lithium ion battery is obtained.
Embodiment 2
(1) Delanium is added after ammoniacal liquor is well mixed with absolute ethyl alcohol, ultrasonic disperse is uniform；
(2) dispersion liquid obtained by step (1) is warming up to 40 DEG C, is then added dropwise butyl titanate, butyl titanate and artificial
The weight ratio of graphite is 5:100, heating stirring reaction 20h；
(3) reaction solution of step (2) is cooled to room temperature, centrifuged, solid product is placed in horse after drying in oven
Not in stove, in 500 DEG C of heat preservation sintering 3h, the graphite negative material of lithium ion battery is obtained.
Fig. 1 is the electron microscope of graphite negative material of lithium ion battery obtained by the present embodiment, can see the graphite of otherwise smooth
Surface modification layer of titanium dioxide.
To examine the performance of the lithium ion battery negative material of the invention prepared, with (the C@TiO of embodiment 120.15) it is and real
Apply (the C@TiO of example 220.05) gained cell negative electrode material prepares lithium ion battery.Wherein negative material:Conductive acetylene is black:PVDF
Thickener is 80:1:1 mass ratio, it is mixed into slurry and is coated on copper foil and was made in dry 12 hours in vacuum drying chamber negative
Pole piece, lithium ion half-cell is formed with lithium piece, electrolyte is 1mol/l LiPF6/ (EC+DME), and barrier film uses
Celgard2400 films (from the barrier film of market purchase), and carried out pair with unmodified Delanium (C) negative electrode lithium ion battery
Than as a result as shown in Figure 2.
After 1 gained cathode material lithium ion battery, 200 cycle charge-discharges of embodiment it can be seen from Fig. 2 results, capacity
Reach 312mAh g-1, and capacity held stationary.The gained negative material of embodiment 2 has certain for the cycle performance of graphite
Improve.
After the present invention is by metatitanic acid lipid cladding and sintering processes, one layer of amorphous titania is formd in graphite surface
Decorative layer, the increase of graphite average grain diameter, obtain a kind of amorphous titania modification graphite cathode material with core shell structure.
Titanium dioxide can provide graphite faster removal lithium embedded passage, and the modification of titanium dioxide can improve the embedding lithium of graphite and put down
Platform.The modification of titanium dioxide can be obviously improved the charge-discharge performance and cycle performance of lithium ion battery.Meanwhile to Delanium
Coated, the suitability of its negative material and electrolyte more preferably, can increase the cycle performance of battery.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of graphite negative material of lithium ion battery, it is characterised in that including following preparation process：
(1) Delanium is added after ammoniacal liquor is well mixed with absolute ethyl alcohol, ultrasonic disperse is uniform；
(2) dispersion liquid obtained by step (1) is warming up to 40~50 DEG C, titanate esters is then added dropwise, heating stirring reacts 12~24h；
(3) reaction solution of step (2) is cooled to room temperature, centrifuged, in 400~500 DEG C of insulations after solid product drying
2~4h is sintered, obtains the graphite negative material of lithium ion battery.
A kind of 2. preparation method of graphite negative material of lithium ion battery according to claim 1, it is characterised in that：Step
(1) mass concentration of ammoniacal liquor described in is 36%~38%.
A kind of 3. preparation method of graphite negative material of lithium ion battery according to claim 1, it is characterised in that：Step
(1) mass concentration of absolute ethyl alcohol described in is 99.8%.
A kind of 4. preparation method of graphite negative material of lithium ion battery according to claim 1, it is characterised in that：Step
(2) titanate esters and the weight ratio that Delanium in step (1) adds in are 5~20:100.
A kind of 5. preparation method of graphite negative material of lithium ion battery according to claim 4, it is characterised in that：It is described
Titanate esters are 5 with the weight ratio that Delanium adds:100.
A kind of 6. preparation method of graphite negative material of lithium ion battery according to claim 1, it is characterised in that：It is described
Metatitanic acid fat refers to tetraisopropyl titanate, butyl titanate or tetraethyl titanate.
A kind of 7. graphite negative material of lithium ion battery, it is characterised in that：Pass through the method described in any one of claim 1~6
It is prepared.
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| CN201710733239.3A CN107482205A (en) | 2017-08-24 | 2017-08-24 | A kind of graphite negative material of lithium ion battery and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108574098A (en) * | 2018-05-16 | 2018-09-25 | 华南师范大学 | A kind of nanometer titanium dioxide-coated graphite lithium ion battery negative material and preparation method thereof |
| CN109346692A (en) * | 2018-10-10 | 2019-02-15 | 青岛泰达华润新能源科技有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN110311105A (en) * | 2019-06-20 | 2019-10-08 | 桑顿新能源科技(长沙)有限公司 | A kind of cathode pole piece slurry and preparation method, cathode pole piece, lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789574A (en) * | 2016-03-04 | 2016-07-20 | 深圳市翔丰华科技有限公司 | Preparation method of high-temperature graphite anode material for lithium-ion battery |
| CN106129344A (en) * | 2016-06-06 | 2016-11-16 | 重庆大学 | A kind of tin ash/Titanium dioxide spherical granule and the preparation method of graphene nano belt composite |
-
2017
- 2017-08-24 CN CN201710733239.3A patent/CN107482205A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789574A (en) * | 2016-03-04 | 2016-07-20 | 深圳市翔丰华科技有限公司 | Preparation method of high-temperature graphite anode material for lithium-ion battery |
| CN106129344A (en) * | 2016-06-06 | 2016-11-16 | 重庆大学 | A kind of tin ash/Titanium dioxide spherical granule and the preparation method of graphene nano belt composite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108574098A (en) * | 2018-05-16 | 2018-09-25 | 华南师范大学 | A kind of nanometer titanium dioxide-coated graphite lithium ion battery negative material and preparation method thereof |
| CN109346692A (en) * | 2018-10-10 | 2019-02-15 | 青岛泰达华润新能源科技有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN109346692B (en) * | 2018-10-10 | 2021-06-04 | 青岛泰达华润新能源科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN110311105A (en) * | 2019-06-20 | 2019-10-08 | 桑顿新能源科技(长沙)有限公司 | A kind of cathode pole piece slurry and preparation method, cathode pole piece, lithium ion battery |
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Application publication date: 20171215 |
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