CN109809399A - A kind of preparation method of composite graphite negative electrode material - Google Patents
A kind of preparation method of composite graphite negative electrode material Download PDFInfo
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- CN109809399A CN109809399A CN201711176249.8A CN201711176249A CN109809399A CN 109809399 A CN109809399 A CN 109809399A CN 201711176249 A CN201711176249 A CN 201711176249A CN 109809399 A CN109809399 A CN 109809399A
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Abstract
The present invention relates to a kind of preparation method of composite graphite negative electrode material, preparation step is as follows: 1) select different Jiao Yuan to be crushed, shaping, under inert gas shielding in carbide furnace low-temperature carbonization；2) carbonized product is uniformly mixed with adhesive, graphitization catalyst, carries out high temperature graphitization, finally product is sieved again and removes bulky grain, gained is composite graphite negative electrode material.Composite graphite negative electrode material preparation method provided by the invention carries out the advantages of surface is modified, can effectively play the two to artificial graphite using adhesive, so that composite graphite negative electrode material of the present invention has the characteristics that compacted density is high, gram volume is high.
Description
Technical field
The invention belongs to lithium ion battery negative material fields, specifically, the present invention relates to a kind of composite graphite negative electrode materials
The preparation method of material.
Background technique
In recent years, universal with the development of mancarried electronic aid and mobile communication, the performance of lithium ion battery is proposed
Higher requirement.As the important component of lithium ion battery, negative electrode material has significant impact to performance of lithium ion battery.
Conventional graphite class negative electrode material has lower lithium insertion/deintercalation current potential, suitable reversible capacity, resourceful, cheap
The advantages that, leading position is occupied in cathode market always.But meanwhile traditional graphite negative electrodes material exists in cyclic process
The problems such as poor circulation, bad high rate performance, this is mainly as graphite type material there are caused by anisotropy, i.e. graphite
There are different physicochemical properties in grain, when lithium ion is embedded in or is deviate from, generate in different directions or not
Same stress, these stress can not cancel out each other, to generate biggish strain in a certain direction, that is, show as expanding.Electricity
Pole expansion reduces fillable amount of the cell active materials in unit volume, to show that capacity reduces and high rate performance is poor
The problem of.Patent publication No. CN104609400A secondary artificial stone made of oily through-stone oil coke is granulated, coats, is bonded
Black particle is raw material a, and little particle natural graphite nodule is raw material b, is made by removal of impurities, spheroidization, cladding, bonding, high temperature cabonization
Composite graphite material, good cycling stability, the advantages that high rate performance is high.But the material is prepared using a large amount of granulation, removal of impurities
Technique can destroy the bonding between composite graphite, while will generate many active surfaces, to increase electrode slice in charge and discharge
Side reaction in the process occurs, while this method preparation process is complicated, and higher cost hardly results in large-scale popularization.
Summary of the invention
Aiming at the problems existing in the prior art, it in order to integrate the advantage of agraphitic carbon and artificial graphite, obtains being compacted close
The composite graphite negative electrode material of degree height, good cycle, the purpose of the present invention is to provide a kind of composite graphite negative electrode materials
Preparation method, to solve the problems mentioned in the above background technology.It is compacted using composite graphite negative electrode material prepared by the present invention
Density is high, gram volume is big and good cycling stability.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of composite graphite negative electrode material, the described method comprises the following steps:
1. Jiao Yuan is crushed, shaping, under inert gas shielding in carbide furnace low-temperature carbonization；
2. carbonized product is uniformly mixed with adhesive, graphitization catalyst, high-temperature catalytic graphitization is carried out；
3. high temperature graphitization product is sieved and removes bulky grain, gained is composite graphite negative electrode material.
Step 1. in, the Jiao Yuanwei needle coke, sponge coke, any one in shot coke or pitch coke or at least two
The combination of kind；
Step 2. in, the adhesive, which refers to, can commonly bond natural stone in common domain in graphite cathode material field
Ink and artificial graphite, and the adhesive of agraphitic carbon can be made after high temperature graphitization, preferably asphalt, coal drip
One of blueness, phenolic resin, epoxy resin, furane resins and furfural resin are a variety of.The asphalt or coal tar pitch
Partial size is preferably 0.1mm or less.Asphalt of the present invention, coal tar pitch, bitumen, phenolic resin, epoxy resin
Asphalt, coal tar pitch, bitumen, phenolic resin, the epoxy resin of this field various specifications all can be selected.
Step 2. in, the graphitization catalyst be preferably one of carbide and oxide of following elements or
A variety of: silicon, iron, tin, phosphorus or boron are more preferably the carbide of silicon and/or the oxide of phosphorus.
Step 2. in, the dosage of the adhesive is the 5% ~ 30% of burnt source quality；The dosage of graphitization catalyst is coke
The 1% ~ 10% of source quality.
Step 1. in, the described low-temperature carbonization processing time is 2-8 hour, and treatment temperature is 800 ~ 1500 DEG C.
Step 2. in, the high-temperature catalytic graphitization processing time be 24-48 hour, treatment temperature be 2800 ~ 3200
℃。
Step 3. in, the screening can guarantee that the quality of batch is uniform, and particle is uniform.
Compared with prior art, the present invention has following advantageous effects:
Compacted density is high；
Good cycling stability；
Synthesis technology is simple, and cost is relatively low.
Detailed description of the invention
Fig. 1 is the electron microscopic picture of 1 composite graphite negative electrode material of the embodiment of the present invention.
Specific embodiment
The present invention is illustrated below with reference to embodiment, the embodiment of the present invention is only used to illustrate the technical scheme of the present invention,
And non-limiting essence of the invention.
Embodiment 1
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) needle coke and sponge coke are crushed, shaping, and after mixing according to the ratio of 1:1, the inertia in carbide furnace
The lower 850 DEG C of carbonization treatment 3h of gas shield, obtain mixture A；
(2) ratio that mixture A, pitch, silicon carbide are 20:2:1 in mass ratio is mixed, is graphitized at being 3000 DEG C in temperature
28h is handled, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.7um is made
Material, half-cell capacity 359.7mAh/g, first charge discharge efficiency 94.1%.
Embodiment 2
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) needle coke and sponge coke are crushed, shaping, and after mixing according to the ratio of 1:1, the inertia in carbide furnace
The lower 850 DEG C of carbonization treatment 3h of gas shield, obtain mixture A；
(2) ratio that mixture A, pitch, silicon carbide are 20:4:1 in mass ratio is mixed, is graphitized at being 3000 DEG C in temperature
28h is handled, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.4um is made
Material, half-cell capacity 360.2mAh/g, first charge discharge efficiency 94.7%.
Embodiment 3
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) needle coke and sponge coke are crushed, shaping, and after mixing according to the ratio of 1:1, the inertia in carbide furnace
The lower 850 DEG C of carbonization treatment 3h of gas shield, obtain mixture A；
(2) ratio that mixture A, pitch, silicon carbide are 10:1:1 in mass ratio is mixed, is graphitized at being 3000 DEG C in temperature
28h is handled, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.9um is made
Material, half-cell capacity 359.2mAh/g, first charge discharge efficiency 94.4%.
Embodiment 4
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) needle coke and sponge coke are crushed, shaping, and after mixing according to the ratio of 1:1, the inertia in carbide furnace
The lower 1050 DEG C of carbonization treatment 3h of gas shield, obtain mixture A；
(2) ratio that mixture A, pitch, silicon carbide are 20:4:1 in mass ratio is mixed, is graphitized at being 3000 DEG C in temperature
28h is handled, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.2um is made
Material, half-cell capacity 360.7mAh/g, first charge discharge efficiency 94.2%.
Embodiment 5
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) needle coke and sponge coke are crushed, shaping, and after mixing according to the ratio of 1:1, the inertia in carbide furnace
The lower 1250 DEG C of carbonization treatment 3h of gas shield, obtain mixture A；
(2) ratio that mixture A, pitch, silicon carbide are 20:4:1 in mass ratio is mixed, is graphitized at being 3000 DEG C in temperature
28h is handled, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.4um is made
Material, half-cell capacity 359.3mAh/g, first charge discharge efficiency 94.4%.
Embodiment 6
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) needle coke is crushed, after shaping, 1050 DEG C of carbonization treatment 3h under inert gas shielding, obtain in carbide furnace
Product A；
(2) ratio that product A, pitch, silicon carbide are 20:4:1 in mass ratio is mixed, at being 3000 DEG C in temperature at graphitization
28h is managed, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.0um is made
Material, half-cell capacity 359.6mAh/g, first charge discharge efficiency 94.5%.
Embodiment 7
A kind of preparation method of composite graphite negative electrode material provided in this embodiment, includes the following steps:
(1) sponge coke is crushed, after shaping, 1050 DEG C of carbonization treatment 3h under inert gas shielding, obtain in carbide furnace
Product A；
(2) ratio that product A, pitch, silicon carbide are 20:4:1 in mass ratio is mixed, at being 3000 DEG C in temperature at graphitization
28h is managed, is cooled to room temperature, obtains mixture B；
(3) mixture B is screened out into coarse granule with 250 purposes, the composite graphite negative electrode that grain diameter is D50=15.8um is made
Material, half-cell capacity 359.1mAh/g, first charge discharge efficiency 94.8%.
Test result when composite graphite negative electrode material prepared by embodiment 1-7 is assembled into half-cell is as shown in table 1.
The composition and experiment condition of 1 composite graphite negative electrode material of table
| Example | Jiao Yuan proportion | Jiao Yuan: adhesive: graphitization catalyst | Carburizing temperature | Partial size (um) | Irreversible capacity (mAh/g) for the first time | Coulombic efficiency (%) for the first time |
| Embodiment 1 | Needle coke: sponge coke=1:1 | 20:2:1 | 850℃ | 15.7 | 359.7 | 94.1 |
| Embodiment 2 | Needle coke: sponge coke=1:1 | 20:4:1 | 850℃ | 15.4 | 360.2 | 94.7 |
| Embodiment 3 | Needle coke: sponge coke=1:1 | 10:1:1 | 850℃ | 15.9 | 359.2 | 94.4 |
| Embodiment 4 | Needle coke: sponge coke=1:1 | 20:4:1 | 1050℃ | 15.2 | 360.7 | 94.2 |
| Embodiment 5 | Needle coke: sponge coke=1:1 | 20:4:1 | 1250℃ | 15.4 | 359.3 | 94.4 |
| Embodiment 6 | Needle coke | 20:4:1 | 1050℃ | 15.0 | 359.6 | 94.5 |
| Embodiment 7 | Sponge coke | 20:4:1 | 1050℃ | 15.8 | 359.1 | 94.8 |
As can be seen from Table 1, the lithium ion battery of the composite graphite negative electrode material comprising being prepared using method of the invention is had
Preferable irreversible capacity and higher coulombic efficiency for the first time for the first time.
The Applicant declares that the present invention illustrates method detailed of the invention by embodiment described above, but the present invention is simultaneously
It is not limited to above-mentioned method detailed, this means that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of each raw material of product of the present invention
Addition, the selection of concrete mode etc., all fall in protection scope of the present invention and the open scope.
Claims (8)
1. a kind of preparation method of composite graphite negative electrode material, which is characterized in that the described method comprises the following steps:
(1) Jiao Yuan is crushed, shaping, under inert gas shielding in carbide furnace low-temperature carbonization；
(2) carbonized product is uniformly mixed with adhesive, graphitization catalyst, carries out high-temperature catalytic graphitization；
(3) high temperature graphitization product is sieved and removes bulky grain, gained is composite graphite negative electrode material.
2. the preparation method of composite graphite negative electrode material according to claim 1, which is characterized in that the Jiao Yuan is needle-shaped
In coke, sponge coke, shot coke or pitch coke any one or at least two combination.
3. the preparation method of composite graphite negative electrode material according to claim 1, which is characterized in that described adhesive is stone
One of oil asphalt, coal tar pitch, bitumen, phenolic resin, epoxy resin are a variety of.
4. the preparation method of composite graphite negative electrode material according to claim 1, which is characterized in that the graphitization catalysis
Agent is at least one of carbide and oxide of following elements: silicon, iron, phosphorus or tin.
5. the preparation method of composite graphite negative electrode material according to claim 4, which is characterized in that graphitization catalyst is
The carbide of silicon and/or the oxide of phosphorus.
6. the preparation method of composite graphite negative electrode material according to claim 1, which is characterized in that the use of described adhesive
Amount is the 5% ~ 30% of burnt source quality；The dosage of the graphitization catalyst is the 1% ~ 10% of burnt source quality.
7. the preparation method of composite graphite negative electrode material according to claim 1, which is characterized in that at the low-temperature carbonization
Managing the time is 2-8 hours, and treatment temperature is 800 ~ 1500 DEG C.
8. the preparation method of composite graphite negative electrode material according to claim 1, which is characterized in that the catalyzed graphitization
Handling the time is 24-48 hours, and treatment temperature is 2800 ~ 3200 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668820A (en) * | 2019-11-18 | 2020-01-10 | 青岛瀚博电子科技有限公司 | Preparation method of high-performance carbon graphite product with superfine structure |
| CN112938958A (en) * | 2021-01-29 | 2021-06-11 | 乌海宝杰新能源材料有限公司 | Surface modification method of negative electrode material |
| CN113422025A (en) * | 2021-06-25 | 2021-09-21 | 洛阳月星新能源科技有限公司 | Natural graphite composite material and preparation method thereof |
| CN113526500A (en) * | 2021-07-20 | 2021-10-22 | 安徽科达新材料有限公司 | Preparation method of high-performance artificial graphite negative electrode material |
| CN115974066A (en) * | 2022-12-29 | 2023-04-18 | 合肥国轩新材料科技有限公司 | Method for preparing artificial graphite by using high-sulfur coke |
| CN117878281A (en) * | 2024-01-09 | 2024-04-12 | 中国华能集团清洁能源技术研究院有限公司 | Negative electrode material, preparation method and application thereof, and lithium ion battery |
| WO2024164649A1 (en) * | 2023-02-08 | 2024-08-15 | 溧阳紫宸新材料科技有限公司 | Catalytic graphite material, preparation method, and use thereof |
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2017
- 2017-11-22 CN CN201711176249.8A patent/CN109809399A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668820A (en) * | 2019-11-18 | 2020-01-10 | 青岛瀚博电子科技有限公司 | Preparation method of high-performance carbon graphite product with superfine structure |
| CN112938958A (en) * | 2021-01-29 | 2021-06-11 | 乌海宝杰新能源材料有限公司 | Surface modification method of negative electrode material |
| CN113422025A (en) * | 2021-06-25 | 2021-09-21 | 洛阳月星新能源科技有限公司 | Natural graphite composite material and preparation method thereof |
| CN113422025B (en) * | 2021-06-25 | 2023-02-03 | 洛阳月星新能源科技有限公司 | Natural graphite composite material and preparation method thereof |
| CN113526500A (en) * | 2021-07-20 | 2021-10-22 | 安徽科达新材料有限公司 | Preparation method of high-performance artificial graphite negative electrode material |
| CN115974066A (en) * | 2022-12-29 | 2023-04-18 | 合肥国轩新材料科技有限公司 | Method for preparing artificial graphite by using high-sulfur coke |
| WO2024164649A1 (en) * | 2023-02-08 | 2024-08-15 | 溧阳紫宸新材料科技有限公司 | Catalytic graphite material, preparation method, and use thereof |
| CN117878281A (en) * | 2024-01-09 | 2024-04-12 | 中国华能集团清洁能源技术研究院有限公司 | Negative electrode material, preparation method and application thereof, and lithium ion battery |
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Application publication date: 20190528 |