CN105958069A - Preparation method of graphite negative electrode material for lithium-ion battery - Google Patents
Preparation method of graphite negative electrode material for lithium-ion battery Download PDFInfo
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- CN105958069A CN105958069A CN201610371249.2A CN201610371249A CN105958069A CN 105958069 A CN105958069 A CN 105958069A CN 201610371249 A CN201610371249 A CN 201610371249A CN 105958069 A CN105958069 A CN 105958069A
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- graphite
- graphite negative
- transition metal
- mixture
- ion battery
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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
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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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- 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 discloses a preparation method of a graphite negative electrode material for a lithium-ion battery, and mainly aims at solving the problem that improvement of existing surface coating on the performance of the graphite negative electrode material, especially improvement of high-current charge-discharge property is not particularly significant in the prior art. The method comprises the following steps of: mixing transition metal carbonate microparticles and graphene oxide evenly; mixing a mixture and a dispersion medium evenly; mixing the mixture and graphite powder evenly; and sequentially drying, roasting, cooling, smashing and screening the mixture to prepare the surface-coated enveloped graphite negative electrode material. Through the scheme, higher tap density and electrical conductivity are achieved; and the reversible specific capacity of the lithium battery prepared from the enveloped graphite negative electrode material is higher.
Description
Technical field
The present invention relates to the negative material of a kind of lithium ion battery, specifically, relate to a kind of lithium-ion electric
The preparation method of pond graphite cathode material.
Background technology
The negative material being now widely used for lithium ion battery is mainly carbon negative pole material；Carbon negative pole material
Electrical property is decided by the many factors such as its internal structure, particle shape, surface nature；Research shows, carbon material
Expect to exist as the negative material of lithium ion battery many deficiencies, and it is not enough and its surface exists substantial amounts of lacking
Falling into and have much relations, the quality of surface nature is for discharging efficiency first, high power charging-discharging ability, electric capacity
Amount etc. all has a major impact；Therefore, carbon negative pole material carries out surface to be treated as improving the effective of its performance
Method；Common carbon negative pole material surface treatment method has cladding process, doping method, oxidation-reduction method, machinery
Polishing etc.；Wherein, with certain carbon materials, for substrate, at its Surface coating, another kind of to have different structure special
The material of point, forms so-called " nucleocapsid " structure through suitable process, obtains the stone of better performance with this
Ink has become the most universal method；But the raising that existing Surface coating is to graphite cathode material performance, especially
Be the improvement of high rate during charging-discharging be not the most particularly significant so that graphite cathode material is at high-end lithium ion
The application of battery is by a definite limitation.
Summary of the invention
The problem to be solved in the present invention is the raising to graphite cathode material performance of the existing Surface coating, particularly
The improvement of high rate during charging-discharging is not the most particularly significant, so that graphite cathode material is at high-end lithium-ion electric
The application in pond is by a definite limitation.
In order to solve the problems referred to above, the present invention provides following technical scheme:
The preparation method of graphite negative material of lithium ion battery comprises the following steps:
A () is by transition metal carbonate micron particle, graphene oxide in mass ratio 0.1～2.8:1.1～7.2
Mix homogeneously；
B the mixture of step (a) is mixed all by () with disperse medium in mass ratio 100～500: 1.2～10.0
Even；
C the mixture of step (b) is mixed by () with graphite powder in mass ratio 101.2～510.0: 90.0～98.8
Uniformly；
D the mixture of step (b) is dried by () after, in inert atmosphere or reduction mixed atmosphere, 350
～constant temperature calcining 5～15 hours at 600 DEG C, constant temperature calcining 6～24 hours at 650～1200 DEG C, then
After being cooled to room temperature with 5～35 DEG C/min cooling rate, after taking out pulverizing, screening, i.e. prepare Surface coating
The graphite cathode material of the peplos of one layer of graphene oxide, transition metal carbonate composition.
Specifically, in described step (b) disperse medium be water, methanol, ethanol, benzene, toluene, acetone,
Organic acid and one or more in organic ester, carry out supersound process or ball-milling treatment in step (c) simultaneously.
Specifically, drying in described step (d) is to carry out at a temperature of 200 DEG C～450 DEG C.
Specifically, in transition metal carbonate micron particle, transition metal is any one in Co, Fe, Mn.
Compared with prior art, the method have the advantages that the present invention with graphite material as kernel,
At graphite material Surface coating by one layer of peplos being made up of graphene oxide, transition metal carbonate；Implement
Example 4 is not added graphene oxide；Embodiment 5 is not added transition metal carbonate micron particle,
Experiment proves to add the peplos that the embodiment 3 of transition metal carbonate micron particle and graphene oxide is made
The tap density of graphite cathode material and conductivity are higher than embodiment 4 and embodiment 5, therefore transition metal carbon
The mixing of graphite powder and graphene oxide is played promotion catalysed promoted effect by hydrochlorate micron particle.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, and embodiments of the present invention include but not limited to
The following example.
Embodiment 1
It is dissolved in 100ml water after the graphene oxide of the cobalt carbonate micron particle of 0.1g, 1.1g is closed uniformly
To mixture, add 98.8g graphite powder in the mixture, after ultrasonic Treatment 2h；At 200 DEG C slowly
Drying, the material after drying is put into and is flushed with hydrogen ball milling in the ball mill container of gas or nitrogen atmosphere is powder body, then
On tablet machine, above-mentioned powder body is made lamellar, be incorporated with in the sintering vessel of lid；Then will be equipped with the burning of material
Knot vessel are placed in sintering furnace, in argon, nitrogen or reduction mixed atmosphere, with the 5 DEG C/min rate of heat addition
Heat up, constant temperature calcining 15h at 350 DEG C, then heat up with the 5 DEG C/min rate of heat addition, roast in 650 DEG C of constant temperature
Burn 24h, after being then cooled to room temperature with 5 DEG C/min rate of temperature fall, after taking out pulverizing, screening, i.e. prepare surface
It is coated with the graphite cathode material of the peplos of one layer of graphene oxide, transition metal carbonate composition；Cobalt carbonate is micro-
Rice grain can be replaced by other transition metal carbonate, such as Fe or Mn.
Embodiment 2
It is dissolved in 300ml water after the graphene oxide of the cobalt carbonate micron particle of 2g, 5g is closed uniformly and being mixed
Compound, adds 93g graphite powder, after ultrasonic Treatment 2h in the mixture；Slowly dry at 300 DEG C,
Material after drying is put into and is flushed with hydrogen ball milling in the ball mill container of gas or nitrogen atmosphere is powder body, then at tablet machine
On above-mentioned powder body is made lamellar, be incorporated with in the sintering vessel of lid；Then will be equipped with the sintering vessel of material
It is placed in sintering furnace, in argon, nitrogen or reduction mixed atmosphere, heats up with the 5 DEG C/min rate of heat addition,
Constant temperature calcining 8h at 400 DEG C, then heat up with the 5 DEG C/min rate of heat addition, in 1000 DEG C of constant temperature calcining 10h,
Then, after being cooled to room temperature with 20 DEG C/min rate of temperature fall, after taking out pulverizing, screening, Surface coating one is i.e. prepared
The graphite cathode material of the peplos that layer graphene oxide, transition metal carbonate form.
Embodiment 3
It is dissolved in 500ml water after the graphene oxide of the cobalt carbonate micron particle of 2.8g, 7.2g is closed uniformly
To mixture, add 90g graphite powder in the mixture, after ultrasonic Treatment 2h；Slowly dry at 450 DEG C
Doing, the material after drying is put into and is flushed with hydrogen ball milling in the ball mill container of gas or nitrogen atmosphere is powder body, then in pressure
On sheet machine, above-mentioned powder body is made lamellar, be incorporated with in the sintering vessel of lid；Then will be equipped with the sintering of material
Vessel are placed in sintering furnace, in argon, nitrogen or reduction mixed atmosphere, with 5 DEG C/min rate of heat addition liter
Temperature, constant temperature calcining 5h at 600 DEG C, then heat up with the 5 DEG C/min rate of heat addition, in 1200 DEG C of constant temperature calcinings
6h, after being then cooled to room temperature with 35 DEG C/min rate of temperature fall, i.e. prepares surface bag after taking out pulverizing, screening
Cover the graphite cathode material of the peplos of one layer of graphene oxide, transition metal carbonate composition.
Embodiment 4
The cobalt carbonate micron particle of 2.8g is dissolved in 500ml water and obtains mixture, add in the mixture
90g graphite powder, after ultrasonic Treatment 2h；Slowly drying at 450 DEG C, the material after drying is put into and is filled
In the ball mill container of hydrogen or nitrogen atmosphere, ball milling is powder body, then on tablet machine, above-mentioned powder body is made lamellar,
It is incorporated with in the sintering vessel of lid；Then the sintering vessel that will be equipped with material is placed in sintering furnace, argon,
In nitrogen or reduction mixed atmosphere, heat up with the 5 DEG C/min rate of heat addition, constant temperature calcining 5h at 600 DEG C,
Heat up with the 5 DEG C/min rate of heat addition again, in 1200 DEG C of constant temperature calcining 6h, then lower the temperature speed with 35 DEG C/min
After rate is cooled to room temperature, after taking out pulverizing, screening, i.e. prepare one layer of graphene oxide of Surface coating, transition gold
Belong to the graphite cathode material of the peplos of carbonate composition.
Embodiment 5
It is dissolved in 500ml water after the graphene oxide of 7.2g is closed uniformly and obtains mixture, add in the mixture
Enter 90g graphite powder, after ultrasonic Treatment 2h；Slowly drying at 450 DEG C, the material after drying is put into
Being flushed with hydrogen ball milling in the ball mill container of gas or nitrogen atmosphere is powder body, then on tablet machine, above-mentioned powder body is made sheet
Shape, is incorporated with in the sintering vessel of lid；Then the sintering vessel that will be equipped with material is placed in sintering furnace, at argon
In gas, nitrogen or reduction mixed atmosphere, heat up with the 5 DEG C/min rate of heat addition, constant temperature calcining at 600 DEG C
5h, then heat up with the 5 DEG C/min rate of heat addition, in 1200 DEG C of constant temperature calcining 6h, then drop with 35 DEG C/min
After temperature speed is cooled to room temperature, after taking out pulverizing, screening, i.e. prepare Surface coating one layer of graphene oxide, mistake
Cross the graphite cathode material of the peplos of metal carbonate composition.
One layer of graphene oxide of the Surface coating that Example 1 to embodiment 5 is made respectively, transition metal carbon
The graphite cathode material 100g of the peplos of hydrochlorate composition, measures its tap density by tap density meter；Separately take
Example 1 to embodiment 5 is made respectively Surface coating one layer graphene, polyvinyl alcohol, Nanoscale Iron group
The graphite cathode material 100g of the peplos become, measures its conductivity by conductivity of graphite tester.
Graphite cathode material, the tap density of embodiment 1 to embodiment 5 and conductivity before uncoated peplos
Test result such as following table:
Interpretation of result: the tap density of the graphite cathode material that embodiment 1 to embodiment 5 is made and conductivity
All exceed much than the graphite cathode material before uncoated peplos；Therefore graphene oxide, transition metal carbonate
The peplos of composition can increase tap density and the conductivity of graphite cathode material；Embodiment 1 to embodiment 3
It is the most close that tap density and conductivity are the same order of magnitude；In embodiment 3, embodiment 4, embodiment 5,
Graphite cathode material tap density and conductivity that embodiment 4 and embodiment 5 are made are below embodiment 3；
Embodiment 4 is not added graphene oxide；Embodiment 5 is not added transition metal carbonate micron
Grain；Add the peplos graphite that the embodiment 3 of transition metal carbonate micron particle and graphene oxide is made
The tap density of negative material and conductivity are higher than embodiment 4 and embodiment 5, therefore transition metal carbonate
The mixing of graphite powder and graphene oxide is played promotion catalysed promoted effect by micron particle.
At 25 scholar 2 DEG C, the graphite cathode material that Example 1 to embodiment 7 is made respectively makes correspondence
Lithium ion battery carry out constant current charge-discharge test in 0.001V～3.0V voltage range, each embodiment is respectively
To reversible specific capacity during 0.2C multiplying power discharging.
Graphite cathode material, the tap density of embodiment 1 to embodiment 7 and conductivity before uncoated peplos
Test result such as following table:
Interpretation of result: the reversible specific capacity of the graphite cathode material that embodiment 1 to embodiment 3 is made all ratios are not
Graphite cathode material before cladding peplos exceeds a lot；Therefore graphene oxide, transition metal carbonate composition
Peplos can increase the reversible specific capacity of graphite cathode material；Add transition metal carbonate micron particle and oxygen
The tap density of the peplos graphite cathode material that the embodiment 3 of functionalized graphene is made and conductivity are than embodiment 4
With the height of embodiment 5, therefore the mixing of graphite powder and graphene oxide is risen by transition metal carbonate micron particle
Promote catalysed promoted effect.
According to above-described embodiment, the present invention just can be realized well.What deserves to be explained is, based on said structure
On the premise of design, for solving same technical problem, even if some made in the present invention are without substantive
Change or polishing, the essence of the technical scheme used still as the present invention, therefore its should also be as this
In the protection domain of invention.
Claims (4)
1. the preparation method of a graphite negative material of lithium ion battery, it is characterised in that comprise the following steps:
A () is by transition metal carbonate micron particle, graphene oxide in mass ratio 0.1～2.8:1.1～7.2
Mix homogeneously；
B the mixture of step (a) is mixed all by () with disperse medium in mass ratio 100～500: 1.2～10.0
Even；
C the mixture of step (b) is mixed by () with graphite powder in mass ratio 101.2～510.0: 90.0～98.8
Uniformly；
D the mixture of step (b) is dried by () after, in inert atmosphere or reduction mixed atmosphere, 350
～constant temperature calcining 5～15 hours at 600 DEG C, constant temperature calcining 6～24 hours at 650～1200 DEG C, then
After being cooled to room temperature with 5～35 DEG C/min cooling rate, after taking out pulverizing, screening, i.e. prepare Surface coating
The graphite cathode material of the peplos of one layer of graphene oxide, transition metal carbonate composition.
The preparation method of graphite negative material of lithium ion battery the most according to claim 1, its feature exists
In, in described step (b) disperse medium be water, methanol, ethanol, benzene, toluene, acetone, organic acid with
One or more in organic ester, carry out supersound process or ball-milling treatment in step (c) simultaneously.
The preparation method of graphite negative material of lithium ion battery the most according to claim 1, its feature exists
In, drying in described step (d) is to carry out at a temperature of 200 DEG C～450 DEG C.
The preparation method of graphite negative material of lithium ion battery the most according to claim 1, its feature exists
In, during in transition metal carbonate micron particle, transition metal is Co, Fe, Mn any one.
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| CN201610371249.2A CN105958069A (en) | 2016-05-27 | 2016-05-27 | Preparation method of graphite negative electrode material for lithium-ion battery |
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| CN201610371249.2A CN105958069A (en) | 2016-05-27 | 2016-05-27 | Preparation method of graphite negative electrode material for lithium-ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114220955A (en) * | 2021-12-02 | 2022-03-22 | 温州大学新材料与产业技术研究院 | Submicron rod-like cobalt carbonate composite graphene high-performance lithium storage material and lithium ion battery |
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| CN101442123A (en) * | 2007-11-21 | 2009-05-27 | 比亚迪股份有限公司 | Composite material for lithium ion battery cathode and preparation method thereof as well as cathode and battery |
| CN102903898A (en) * | 2012-10-19 | 2013-01-30 | 山东大学 | Graphite and transitional metallic oxide composite cathode material and preparation method thereof |
| CN104868106A (en) * | 2015-04-21 | 2015-08-26 | 常州第六元素材料科技股份有限公司 | Method for coating graphite anode material of lithium ion battery with graphene and application thereof |
-
2016
- 2016-05-27 CN CN201610371249.2A patent/CN105958069A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101442123A (en) * | 2007-11-21 | 2009-05-27 | 比亚迪股份有限公司 | Composite material for lithium ion battery cathode and preparation method thereof as well as cathode and battery |
| CN102903898A (en) * | 2012-10-19 | 2013-01-30 | 山东大学 | Graphite and transitional metallic oxide composite cathode material and preparation method thereof |
| CN104868106A (en) * | 2015-04-21 | 2015-08-26 | 常州第六元素材料科技股份有限公司 | Method for coating graphite anode material of lithium ion battery with graphene and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114220955A (en) * | 2021-12-02 | 2022-03-22 | 温州大学新材料与产业技术研究院 | Submicron rod-like cobalt carbonate composite graphene high-performance lithium storage material and lithium ion battery |
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| CB03 | Change of inventor or designer information |
Inventor after: Liu Ziqian Inventor after: Chen Rui Inventor after: Zeng Dingjun Inventor after: Liu Xinyao Inventor before: Liu Ziqian Inventor before: Liu Xinyao |
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Application publication date: 20160921 |
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