CN109585821A - Graphite composite material, preparation method, application and negative electrode of lithium ion battery - Google Patents

Graphite composite material, preparation method, application and negative electrode of lithium ion battery Download PDF

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Publication number
CN109585821A
CN109585821A CN201811403674.0A CN201811403674A CN109585821A CN 109585821 A CN109585821 A CN 109585821A CN 201811403674 A CN201811403674 A CN 201811403674A CN 109585821 A CN109585821 A CN 109585821A
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graphite
composite material
preparation
lithium ion
ion battery
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张云
罗航
吴昊
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Sichuan University
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Sichuan University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to battery cathode related fieldss, and in particular to graphite composite material, preparation method, application and negative electrode of lithium ion battery.The graphite composite material includes the graphite of 60%-80% weight percent and the graphene of 20%-40% weight percent.The capacity boost of composite material obtained by the application is obvious, can preferably be applied to prepare negative electrode of lithium ion battery.

Description

Graphite composite material, preparation method, application and negative electrode of lithium ion battery
Technical field
The present invention relates to battery cathode related fieldss, and in particular to graphite composite material, preparation method, application And negative electrode of lithium ion battery.
Background technique
Lithium battery can be divided into lithium metal battery and lithium ion battery at present, and wherein the application range of lithium ion battery is wider, Such as the electronic devices such as calculator, notebook, mobile communication equipment.
Lithium ion battery is usually to use lithium ion as anode, therein using carbon material as battery cathode Carbon material can be the materials such as graphite, carbon fiber.Graphite therein is since raw material are easy to get, and cost is relatively low, typically as The negative electrode material of lithium ion battery uses, but since graphite material itself limits, relatively low capacity gradually cannot Meets the needs of today's society is to high-capacity battery.Therefore, usually there is Surface Oxygen to the processing method that graphite is modified at present Change, surface cladding etc., but also have certain limitation to the promotion effect of its capacity.
Summary of the invention
In view of this, the application provides a kind of graphite composite material, preparation method, application and lithium ion battery The capacity boost of cathode, gained composite material is obvious, can preferably be applied to prepare negative electrode of lithium ion battery.
In view of the deficiencies of the prior art, the present invention provides the technical solutions of first aspect, i.e. graphite composite wood Material, the graphene of graphite and 20%-40% weight percent including 60%-80% weight percent.
Optionally, the particle size of the graphite is 5 μm -200 μm.
The application also provides the technical solution of second aspect, i.e. graphite-graphene composite material preparation method, including with Lower step:
1) through ball milling after being mixed in a certain ratio graphite and grinding aid, dispersing agent, while a period of time is stirred by ultrasonic, obtains Obtain mixed slurry;The ratio of graphite and grinding aid is (1-4): 1, the concentration that graphite and grinding aid are formed in dispersing agent is 2mg/ mL-5mg/mL;
2) mixed slurry obtained by step 1) is placed in natural cooling under low temperature environment, after be freeze-dried, obtain graphite- Graphene composite material.
Optionally, the grinding aid is more fragrant type organics.
Optionally, the grinding aid is N- methyl-pyrrolidon NMP or n,N-Dimethylformamide DMF.
Optionally, the dispersing agent is water.
It optionally, is 1h-8h for a period of time described in step 1).
Optionally, in step 2) time of natural cooling be for 24 hours -48h, the time of freeze-drying be 20h-24h.
Optionally, low temperature environment is 15 DEG C -20 DEG C of temperature environment in step 2).
The application also provides the technical solution of the third aspect, i.e. graphite composite material, according to aforementioned any institute The preparation method stated is prepared.
Optionally, the graphene of graphite and 20%-40% weight percent including 60%-80% weight percent.
Optionally, the particle size of the graphite is 5 μm -200 μm.
The application also provides the technical solution of fourth aspect, i.e., aforementioned any graphite composite material exists Prepare the application of negative electrode of lithium ion battery.
The application also provides the technical solution of the 5th aspect, i.e. negative electrode of lithium ion battery, using aforementioned any stone Ink/graphene composite material is prepared.
Scheme provided by the present invention mainly by using graphite composite material, preparation method, application and lithium from Sub- battery cathode, gained composite material is compound with graphene using graphite, improves its capacitance, hence it is evident that higher than graphite itself Capacitance can preferably be applied to prepare negative electrode of lithium ion battery.
Material or component used by the application are routinely component, can buy acquisition in the market.
Detailed description of the invention
Fig. 1 is the electron scanning map of 17 gained composite material of embodiment;
Fig. 2 is the XRD spectrum of embodiment 17 gained composite material and 1 resulting materials of embodiment;
Fig. 3 is that the first charge-discharge for the negative electrode of lithium ion battery that embodiment 17 is prepared respectively with 1 resulting materials of embodiment is bent Line chart comparison diagram;
Fig. 4 is that the negative electrode of lithium ion battery that embodiment 17 and embodiment 1 are prepared respectively divides at 0.1C, 1C, 2C, 5C, 10C The charge/discharge capacity curve comparison figure not being recycled;
Fig. 5 is filling of being recycled at 1C of the negative electrode of lithium ion battery that embodiment 17 is prepared respectively with embodiment 1 Discharge capacity curve comparison figure.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with embodiment of the present invention, Technical solution in embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only this Invent a part of embodiment, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill Personnel's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.In the absence of conflict, the feature in the embodiment and embodiment in the present invention can mutual any combination.
Following every embodiment party can be used in graphite composite material and negative electrode of lithium ion battery described herein Different preparation methods in formula obtain the graphite composite material and negative electrode of lithium ion battery of each embodiment.
Embodiment one
According to the following steps and the parameters of table 1 prepare the graphite composite material of each embodiment respectively.
1) through ball milling after being mixed in a certain ratio graphite and grinding aid, dispersing agent, while a period of time T1/ is stirred by ultrasonic H obtains mixed slurry;The ratio of graphite and grinding aid A are D1, and graphite is with the grinding aid A concentration formed in dispersant B D2/mg/mL。
2) mixed slurry obtained by step 1) is placed in natural cooling T2/h in the environment of t/ DEG C of temperature, after be freeze-dried T3/h obtains graphite-graphene composite material.
2) the graphite composite material of resulting each embodiment is used to prepare negative electrode of lithium ion battery, can be used This field customary preparation methods, and gained graphite composite material is detected using UV absorption, obtain its ingredient Content value, the weight percent L2/% of weight percent L1/% and graphene including graphite, wherein the particle size of graphite It is h/ μm, while lithium ion battery is made with other conventional materials in the negative electrode of lithium ion battery being accordingly prepared, measures it First charge-discharge capacity Q1/mAhg under cathode 1C-1, recycle at 1C charge/discharge capacity Q2/mAhg several times-1, in 1C The charge/discharge capacity Q3/mAhg that lower circulation is 100 times-1, gained measured value such as table 2.
Table 1
Embodiment A B T1/h D1 D2/mg/mL t/℃ T2/h T3/h
1 NMP Ethyl alcohol 0.5 0.5:1 2 25 20 15
2 NMP Ethyl alcohol 0.8 5:1 5 22 15 17
3 NMP Ethyl alcohol 9 6:1 1 10 50 26
4 NMP Ethyl alcohol 10 8:1 10 12 52 28
5 NMP Ethyl alcohol 0.5 1:1 2 25 20 15
6 NMP Ethyl alcohol 0.8 4:1 3 22 15 17
7 NMP Ethyl alcohol 9 2:1 4 10 50 26
8 NMP Ethyl alcohol 10 3:1 5 12 52 28
9 DMF Ethyl alcohol 0.5 0.5:1 2 25 20 15
10 DMF Ethyl alcohol 0.8 5:1 5 22 15 17
11 DMF Ethyl alcohol 9 6:1 1 10 50 26
12 DMF Ethyl alcohol 10 8:1 10 12 52 28
13 DMF Ethyl alcohol 0.5 1:1 2 25 20 15
14 DMF Ethyl alcohol 0.8 4:1 3 22 15 17
15 DMF Ethyl alcohol 9 2:1 4 10 50 26
16 DMF Ethyl alcohol 10 3:1 5 12 52 28
Table 2
Embodiment L1/% L2/% h/μm Q1/mAh·g-1 Q2/mAh·g-1 Q3/mAh·g-1
1 20 80 300 391 353 320
2 90 10 250 350 335 292
3 92 8 270 351 336 290
4 100 0 300 355 340 300
5 60 40 300 398 395 391
6 70 30 300 397 396 396
7 75 25 260 398 395 391
8 80 20 260 397 396 396
9 20 80 300 391 353 320
10 90 10 250 350 335 292
11 92 8 270 351 336 290
12 100 0 300 355 340 300
13 60 40 300 398 395 391
14 70 30 300 397 396 396
15 75 25 260 398 395 391
16 80 20 260 397 396 396
Embodiment two
According to the following steps and the parameters of table 3 prepare the graphite composite material of each embodiment respectively.
1) through ball milling after being mixed in a certain ratio graphite and grinding aid, dispersing agent, while a period of time T1/ is stirred by ultrasonic H obtains mixed slurry;The ratio of graphite and grinding aid A are D1, and graphite is with the grinding aid A concentration formed in dispersant B D2/mg/mL。
2) mixed slurry obtained by step 1) is placed in natural cooling T2/h in the environment of t/ DEG C of temperature, after be freeze-dried T3/h obtains graphite-graphene composite material.
2) the graphite composite material of resulting each embodiment is used to prepare negative electrode of lithium ion battery, can be used This field customary preparation methods, and gained graphite composite material is accordingly detected, its component content value is obtained, The weight percent L2/% of weight percent L1/% and graphene including graphite, wherein the particle size of graphite is h/ μm, Lithium ion battery is made with other conventional materials in the negative electrode of lithium ion battery being accordingly prepared simultaneously, is measured under its cathode 1C First charge-discharge capacity Q1/mAhg-1, recycle at 1C charge/discharge capacity Q2/mAhg several times-1, recycled at 1C 100 charge/discharge capacity Q3/mAhg-1, gained measured value such as table 4.
Table 3
Embodiment A B T1/h D1 D2/mg/mL t/℃ T2/h T3/h
17 NMP Water 1 1:1 2 20 24 20
18 NMP Water 8 4:1 3 18 30 21
19 NMP Water 5 2:1 4 17 40 22
20 NMP Water 6 3:1 5 15 48 24
21 DMF Water 1 1:1 2 20 24 20
22 DMF Water 8 4:1 3 18 30 21
23 DMF Water 5 2:1 4 17 40 22
24 DMF Water 6 3:1 5 15 48 24
Table 4
It can be concluded that, made used by embodiment 1-4,9-12 in table 1 and table 2 from above table and subsequent drawings Preparation Method is variant with the application, and for resulting materials after being applied to prepare negative electrode of lithium ion battery, charge/discharge capacity is obvious The negative electrode of lithium ion battery being prepared lower than embodiment 5-8, embodiment 13-16 resulting materials.
Embodiment in table 3 and table 4 uses preparation method described herein, and gained composite material is being applied to preparation After negative electrode of lithium ion battery, charge/discharge capacity is apparently higher than negative electrode of lithium ion battery prepared by graphite material, compares simultaneously For the more material of graphene, for the application composite material in the case where being recycled for multiple times, charge/discharge capacity is more stable.
Shown in the drawings, Fig. 1 is the electron scanning map of 17 gained composite material of embodiment;Fig. 2 is 17 institute of embodiment Obtain the XRD spectrum of composite material and 1 resulting materials of embodiment;Fig. 3 is that embodiment 17 is prepared respectively with 1 resulting materials of embodiment The first charge-discharge curve graph comparison diagram of negative electrode of lithium ion battery;Fig. 4 is the lithium ion that embodiment 17 and embodiment 1 are prepared respectively The charge/discharge capacity curve comparison figure that battery cathode is recycled respectively at 0.1C, 1C, 2C, 5C, 10C;Fig. 5 is to implement The charge/discharge capacity curve comparison that the negative electrode of lithium ion battery that example 17 and embodiment 1 are prepared respectively is recycled at 1C Figure.It can also clearly be obtained from attached drawing, graphite/stone described herein can more preferably be obtained using the application preparation method Black alkene composite material, and gained composite material, after being applied to prepare negative electrode of lithium ion battery, charge/discharge capacity is obviously excellent Graphite material itself is also apparently higher than in the stability of the charge/discharge capacity of graphite material itself, and its charge/discharge capacity.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change It also should be regarded as protection scope of the present invention into retouching.

Claims (10)

1. graphite composite material, it is characterised in that: graphite and 20%-40% including 60%-80% weight percent The graphene of weight percent.
2. graphite composite material according to claim 1, it is characterised in that: the particle size of the graphite is 5 μm-200μm。
3. the preparation method of graphite composite material, which comprises the following steps:
1) through ball milling after being mixed in a certain ratio graphite and grinding aid, dispersing agent, while a period of time is stirred by ultrasonic, is mixed Close slurry;The ratio of graphite and grinding aid is (1-4): 1, the concentration that graphite and grinding aid are formed in dispersing agent is 2mg/mL- 5mg/mL;
2) mixed slurry obtained by step 1) is placed in natural cooling under 15 DEG C -20 DEG C of temperature environment, after be freeze-dried, obtain To graphite-graphene composite material.
4. preparation method according to claim 3, it is characterised in that: the grinding aid be N- methyl-pyrrolidon NMP or N,N-Dimethylformamide DMF.
5. preparation method according to claim 3, it is characterised in that: be 1h-8h for a period of time described in step 1).
6. preparation method according to claim 3, it is characterised in that: the time of natural cooling is -48h for 24 hours in step 2), The time of freeze-drying is 20h-24h.
7. graphite composite material, it is characterised in that: it is prepared according to preparation method described in power 3.
8. graphite composite material according to claim 7, it is characterised in that: including 60%-80% weight percent The graphite of ratio and the graphene of 20%-40% weight percent.
9. any graphite composite material of power 1, power 7 is in the application for preparing negative electrode of lithium ion battery.
10. negative electrode of lithium ion battery, it is characterised in that: using power 1, any graphite composite material preparation of power 7 It forms.
CN201811403674.0A 2018-11-23 2018-11-23 Graphite composite material, preparation method, application and negative electrode of lithium ion battery Pending CN109585821A (en)

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Cited By (1)

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CN113809299A (en) * 2021-09-14 2021-12-17 远景动力技术(江苏)有限公司 Negative electrode active material, negative electrode sheet, preparation method and application of negative electrode sheet

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Application publication date: 20190405