WO2022063292A1 - 石墨烯导电复合材料及其制备方法和应用以及锂离子电池 - Google Patents
石墨烯导电复合材料及其制备方法和应用以及锂离子电池 Download PDFInfo
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- WO2022063292A1 WO2022063292A1 PCT/CN2021/120911 CN2021120911W WO2022063292A1 WO 2022063292 A1 WO2022063292 A1 WO 2022063292A1 CN 2021120911 W CN2021120911 W CN 2021120911W WO 2022063292 A1 WO2022063292 A1 WO 2022063292A1
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Definitions
- the invention relates to the field of lithium ion batteries, in particular to a graphene conductive composite material, a preparation method and application thereof, and a lithium ion battery.
- graphene As a new type of conductive agent, graphene has a two-dimensional sheet structure, which makes it have a lower conductivity threshold, which can significantly reduce the internal resistance of the battery and improve the rate performance; and has high flexibility, which can effectively alleviate the charging and discharging process. Volume expansion improves battery cycle performance, so it is widely used in lithium battery conductive agents.
- CN109824041A provides a graphene conductive agent for lithium batteries and a preparation method thereof, wherein a certain quality of graphite, a dispersant and a solvent are separated by ball milling and screen vibration to obtain a graphene conductive agent, and its use as a positive electrode additive is significantly improved
- the comprehensive properties of lithium cobalt oxide cathode materials were investigated.
- CN108975322A discloses a method for preparing graphene slurry, wherein expanded graphite is soaked in a dispersion medium and stirred, and then ultrasonically exfoliated to obtain graphene slurry. It has been found that the graphene conductive paste prepared by passing graphite and solvent through a ball mill, high pressure homogenizer or ultrasonic is easy to agglomerate, the stability of the paste is poor and the graphene sheet is thick, so it is considered to be of poor quality.
- CN111509226A discloses a graphene with carbon nanotubes grown on the surface, wherein the grafted carbon nanotubes convert the two-dimensional structure of graphene into a three-dimensional structure material, thereby suppressing the stacking problem of graphene.
- this process has high requirements on the raw material graphene, and the process is complicated, which is not conducive to industrial production.
- the purpose of the present invention is to solve one or more problems of graphene composite materials in the prior art, such as uneven dispersion in a solvent, easy agglomeration, and thickness of lamellae.
- the present invention provides a new graphene conductive composite material, a preparation method and application thereof, and a lithium ion battery containing the graphene conductive composite material.
- the graphene conductive composite material of the present invention has good dispersibility in organic solvents, is not easy to agglomerate, and has significantly improved electrical conductivity.
- a first aspect of the present invention relates to a graphene conductive composite material
- the graphene conductive composite material includes graphene nanosheets and a conjugated copolymer, wherein the conjugated copolymer contains an alkyne group, has a linear structure, and is combined with graphene nanosheets. slice graft.
- the second aspect of the present invention relates to a method for preparing a graphene conductive composite material, the graphene conductive composite material includes graphene nanosheets and a conjugated copolymer, wherein the conjugated copolymer contains an alkyne group, has a linear structure, and is combined with Graphene nano-sheet grafting, the method comprises the following steps:
- Graphene nanosheets were pretreated with 4-bromoboronic acid diazobenzene tetrafluoroborate, and conjugated copolymers were formed in the presence of the pretreated graphene nanosheets.
- the third aspect of the present invention relates to the graphene conductive composite material prepared by the above preparation method.
- the fourth aspect of the present invention relates to the application of the above-mentioned graphene conductive composite material in a lithium ion battery.
- a fifth aspect of the present invention relates to a lithium ion battery
- the lithium ion battery includes a negative electrode comprising the graphene conductive composite material provided by the present invention and a silicon-containing negative electrode material, a positive electrode comprising a lithium-containing positive electrode material, a separator and an electrolytic liquid.
- the graphene conductive composite material provided by the present invention is grafted with a conjugated copolymer on the graphene nanosheet.
- the grafted conjugated copolymer acts as a "barrier layer” to inhibit the agglomeration and stacking between graphene nanosheets and improve the dispersibility of the material in the solvent.
- the conjugated moiety in the conjugated copolymer is connected by an alkynyl group, which opens up the electron transfer channel, which is beneficial to the electron transfer between the graphene nanosheet and the conjugated copolymer and in the conjugated copolymer. transmission.
- the grafted conjugated copolymer also acts as a "conductive brush", thereby reducing the conduction threshold of graphene nanosheets and extending the conductive structure of graphene nanosheets, extending the two-dimensional conductive plane to three-dimensional space .
- the flexible structure derived from graphene nanosheets can also buffer the volume expansion of silicon-containing anode materials during charging and discharging, thereby improving the structural stability of the anode and improving the overall performance of the anode, so that it can be used in lithium ion applications. It can improve the rate performance and cycle stability of lithium batteries when in batteries.
- the graphene conductive composite material is prepared by the present invention
- 4-bromoboric acid diazobenzene tetrafluoroborate is used to pretreat the graphene nanosheets, and halogen functional groups (bromine, iodine, etc.) are introduced on the graphene nanosheets, Then, the conjugated copolymer is grafted by the coupling reaction between the halogen and the conjugated copolymer. In this way, the grafted conjugated copolymer is uniformly distributed on the surface of graphene nanosheets, and, combined with the selection of monomers, the conjugated copolymer has a linear structure.
- the preparation process provided by the present invention has no requirements on the type of graphene nanosheets as raw materials, and the process is simple and convenient, so it is more suitable for industrial production.
- Fig. 1 is the structural representation of the graphene conductive composite material obtained in Example 1, wherein A is graphene, and B is conjugated copolymer;
- Fig. 2 is the infrared spectrogram of gained A-1, A-2 and A-3 in embodiment 1;
- Fig. 3 is the SEM image of the graphene conductive composite material obtained in Example 1;
- Fig. 4 is the SEM image of raw material graphene nanosheet in embodiment 1;
- Fig. 5 is the SEM image of gained A-3 in embodiment 1;
- FIG. 8 is a rate cycle graph of the batteries obtained in Application Example 1 and Application Example 2.
- FIG. 8 is a rate cycle graph of the batteries obtained in Application Example 1 and Application Example 2.
- graphene refers to a two -dimensional material consisting of a single layer of sp hybridized carbon atoms packed into a honeycomb structure. Graphene is usually prepared by mechanical exfoliation method, redox method, SiC epitaxial growth method, etc. Thus, the term “graphene” also includes graphene oxide, reduced graphene oxide, and the like.
- graphene nanosheet refers to a layered assembly of graphene, which may contain one to ten layers of graphene.
- the graphene nanosheets include single-layer graphene (which may be simply referred to as graphene), double-layer graphene, and few-layer graphene, wherein the few-layer graphene includes 3-10 layers of graphene. It is generally believed that when the number of layers is less than or equal to 10 layers, the layered assembly of graphene has properties similar to graphene (single-layer graphene), so it is named graphene nanosheets. When the number of layers exceeds 10, the performance of the layered assembly of graphene is similar to that of graphite.
- the thickness of graphene nanosheets is on the nanometer scale, and the other two dimensions are usually larger than the nanoscale. In one variation, the graphene nanosheets have a planar dimension of 0.05-5.0 ⁇ m.
- the plane dimension refers to the maximum radial dimension of the material on the X-Y plane.
- the plane dimension of the graphene nanosheets can be obtained by characterization by scanning electron microscopy or atomic force microscopy.
- the present invention provides a graphene conductive composite material, the graphene conductive composite material includes graphene nanosheets and a conjugated copolymer, wherein the conjugated copolymer contains an alkyne group, has a linear structure, and is combined with graphite Grafting of alkene nanosheets.
- the specific surface area of the graphene conductive composite material is 50-300 m 2 /g, preferably 100-250 m 2 /g.
- the electrical conductivity of the graphene composite material is 200-800 S/cm.
- the Raman spectrum of the graphene conductive composite material has a D peak and a G peak, the peak heights of which are ID and IG , respectively, wherein ID/ IG is below 0.50.
- ID/ IG may be 0.01-0.50, preferably 0.03-0.30 , such as but not limited to 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25 , 0.30, 0.35, 0.40, 0.45, 0.50, etc.
- the Raman spectrum of graphene material consists of several peaks, mainly G peak, D peak and G' peak.
- the G peak is the main characteristic peak of graphene, which is caused by the in - plane vibration of sp hybridized carbon atoms, and this peak can effectively reflect the number of graphene layers of graphene samples.
- the D peak is generally considered to be the disordered vibrational peak of graphene and is used to characterize structural defects in graphene samples.
- the G' peak also known as the 2D peak, is a two-phonon resonance second-order Raman peak used to characterize the interlayer stacking pattern of carbon atoms in graphene samples.
- D peak appears in the wavelength range of 1250-1450cm -1 , and its peak height is 1 D ;
- G peak appears in the wavelength range of 1500-1700cm -1 , and its peak height is 1 G ; and a 2D peak appears in the wavelength range of 2600-2800 cm ⁇ 1 with a peak height of I 2D .
- Raman spectroscopy has advantages in characterizing defects in graphene materials. It is generally believed that the defect density is proportional to ID/ IG .
- the graphene conductive composite material has a lower ID / IG , reflecting its characteristics of fewer defects.
- the mass content of the graphene nanosheets is 75%-99%, preferably 85%-99%, and the mass content of the conjugated copolymer is 1%- 25%, preferably 1%-15%.
- Described graphene nanosheet is few-layer graphene, and preferably few-layer graphene comprises 3-5 layers of graphene.
- the Raman spectrum of the graphene nanosheet has a D peak and a G peak, and the peak heights thereof are ID and IG respectively, wherein ID/ IG is below 0.50.
- ID/ IG may be 0.01-0.50, preferably 0.03-0.30 , such as but not limited to 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25 , 0.30, 0.35, 0.40, 0.45, 0.50, etc.
- a D peak appears in the wavelength range of 1250-1450 cm -1 , and its peak height is ID; and a G peak appears in the 1500-1700 cm -1 wavelength range, and its peak height is 1 G ; and a 2D peak appears in the wavelength range of 2600-2800 cm -1 with a peak height of I 2D .
- the graphene nanosheets have lower ID/IG , reflecting that they have fewer defects.
- the graphene nanosheets are commercially available, and can also be prepared according to methods known in the art.
- the graphene nanosheets are prepared as follows:
- step (2) mixing the pre-expanded graphite obtained in step (1), aliphatic amine polyoxyethylene ether and water, successively through the first high-pressure homogenization treatment and the second high-pressure homogenization treatment, to obtain a stack containing graphene nanosheets wherein, the pressure of the first high-pressure homogenization treatment is 30-40MPa, the treatment time is 20-60min, the pressure of the second high-pressure homogenization treatment is 40-50MPa, and the pressure of the second high-pressure homogenization treatment It is 10-20MPa higher than the pressure of the first high-pressure homogenization treatment, and the treatment time is 10-30min;
- step (3) The slurry obtained in step (2) is dried to obtain a stack of graphene nanosheets.
- the expansion ratio of the pre-expanded graphite obtained in step (1) is 200-300 times compared to the expandable graphite.
- the alkynyl group is linked to a conjugated moiety, and the conjugated moiety includes a conjugated group, such as a group each independently selected from a benzene ring, a polycyclic aromatic hydrocarbon, an aromatic heterocyclic ring, and the like.
- the conjugated copolymer is polyaryne copolymer, polyfluorene copolymer, poly-p-styrene copolymer, poly-p-phenylene vinylene copolymer, polythiophene copolymer, polythiophene derivative copolymer, polypyrrole
- the polyaryne copolymer can be a 1,4-diynylbenzene-triphenylamine copolymer.
- the polyfluorene copolymer may be a 1,4-diynylbenzene-9-hexylfluorene copolymer.
- the polythiophene copolymer may be at least one of 1,4-diynylbenzene-3-hexylthiophene copolymer and 1,4-diynylbenzene-thiophene copolymer.
- the polythiophene derivative copolymer may be a 1,4-diynylbenzene-3,4-ethylenedioxythiophene copolymer.
- the present invention provides a method for preparing a graphene conductive composite material, the graphene conductive composite material includes graphene nanosheets and a conjugated copolymer, wherein the conjugated copolymer contains an alkyne group and has a linear structure, And grafted with graphene nanosheets, the method comprises the following steps:
- Graphene nanosheets were pretreated with 4-bromoboronic acid diazobenzene tetrafluoroborate, and conjugated copolymers were formed in the presence of the pretreated graphene nanosheets.
- the pretreatment is performed as follows: under vigorous stirring, an aqueous solution of 4-bromoboronic acid diazobenzene tetrafluoroborate is added dropwise to the aqueous dispersion of graphene nanosheets at -5°C-40°C. °C temperature for 30min-180min, then solid-liquid separation, washing and drying of the solid to obtain pretreated graphene nanosheets.
- the mass concentration of the aqueous solution of 4-bromoboronic acid diazobenzene tetrafluoroborate is 40%-70%.
- the mass concentration of the graphene nanosheets in the aqueous dispersion of the graphene nanosheets is 5%-50%.
- the aqueous dispersion of the graphene nanosheets is obtained by adding the graphene nanosheets into water and dispersing.
- the dispersion can be carried out by stirring, ultrasonic and other methods.
- the mass ratio of 4-bromoborate diazobenzene tetrafluoroborate to graphene nanosheets is 3-6:1.
- the solid-liquid separation can be carried out by filtration.
- an organic solvent such as acetone can be added before separation for further separation.
- the washing can be washed with organic solvents (such as acetone, dimethylformamide (DMF), etc.) and deionized water.
- the number of washes can be one or more times.
- the drying can be vacuum drying, preferably the drying temperature is 60-80°C, and the drying time is 2-10h.
- the forming of the conjugated copolymer in the presence of the pretreated graphene nanosheets includes: in the presence of a catalyst, a solvent and the pretreated graphene nanosheets, performing a polymerization reaction with a monomer for forming the conjugated copolymer, A graphene conductive composite material is obtained.
- the catalyst is selected from at least one of palladium catalysts (wherein palladium is Pd[0], Pd[I] or Pd[II]) and nickel catalysts (wherein nickel is Ni[0] or Ni[II]).
- the amount of the catalyst used is 0.5%-3.0% of the molar amount of the monomer.
- the monomer for forming the conjugated copolymer includes at least two monomers, wherein the first monomer contains a halogen, the halogen is preferably any one of bromine and iodine, and the second monomer is an alkyne-containing base compounds.
- the molar ratio of the first monomer to the second monomer may be 1:1-1.1.
- the specific monomers can be selected from monomers conventionally used for forming conjugated copolymers.
- the first monomer can be 4,4'-dibromotriphenylamine, 1,4-dibromobenzene, 1,4-diiodobenzene, 2,7-dibromofluorene, 2,7-dibromo-9 -One or more of hexylfluorene, 2,5-dibromothiophene, 2,5-dibromo-3-hexylthiophene, and the like.
- the second monomer may be at least one of 1,4-diethynylbenzene, 1,3-diethynylbenzene, 4,4'-diethynylbiphenyl, and the like.
- the solvent can be at least one of N,N'-dimethylformamide and N-methylpyrrolidone.
- the added mass of the solvent accounts for 1%-10% of the mass of the monomer.
- the polymerization is carried out under the following conditions: under an inert atmosphere, at a temperature of 80-150°C, for 12h-36h.
- the inert atmosphere may be a nitrogen atmosphere.
- the product of the polymerization reaction can be processed using conventional post-processing steps such as solid-liquid separation, washing and drying.
- the solid-liquid separation can be carried out by filtration.
- an organic solvent such as methanol can be added before separation for further separation.
- the washing can use organic solvents (such as methanol) and deionized water as washing liquids.
- One or more washes may be employed.
- the drying can be carried out under vacuum, preferably the drying temperature is 60-80° C., and the drying time is 2-10 h.
- the graphene conductive composite material of the present invention has excellent solvent dispersibility and conductivity, and is particularly suitable for application in lithium ion batteries.
- the present invention provides a lithium ion battery
- the lithium ion battery includes a negative electrode comprising the graphene conductive composite material provided by the present invention and a silicon-containing negative electrode material, a positive electrode comprising a lithium element-containing positive electrode material, a separator and Electrolyte.
- the structure of the lithium ion battery provided according to the present invention may be known to those skilled in the art.
- the separator is located between the positive and negative electrodes.
- the positive electrode contains a positive electrode material
- the negative electrode contains the silicon-containing negative electrode material and the graphene conductive composite material.
- the present invention does not specifically limit the specific composition of the positive electrode material, which may be a lithium-containing positive electrode material conventionally used in the art.
- the separator can be selected from various separators used in lithium-ion batteries known to those skilled in the art, such as polypropylene microporous membranes, polyethylene mats, glass fiber mats, or ultrafine glass fiber papers.
- the electrolyte may be various conventional electrolytes, such as non-aqueous electrolytes.
- the non-aqueous electrolyte solution is a solution of electrolyte lithium salt in a non-aqueous solvent.
- Conventional non-aqueous electrolytes known to those skilled in the art can be used.
- the electrolyte may be selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ) and lithium hexafluorosilicate (LiSiF 6 ). at least one.
- the non-aqueous solvent can be selected from the mixed solution of chain acid ester and cyclic acid ester, wherein chain acid ester can be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), carbonic acid At least one of methylpropyl ester (MPC) and dipropyl carbonate (DPC).
- the cyclic acid ester may be at least one of ethylene carbonate (EC), propylene carbonate (PC), and vinylene carbonate (VC).
- the morphology of the materials was characterized by scanning electron microscopy.
- the scanning electron microscope is a TECNALG2F20 (200kv) type from FEI Company of the United States.
- Test conditions directly press the sample on a sample stage containing conductive tape, and then insert the electron microscope for observation. The observation used a magnification of 8000 times.
- the electrochemical performance of the assembled lithium ion batteries was tested by using the Wuhan Blue Electric Battery Test System (CT2001B). Test conditions include: voltage range 0.005V-3V, current range 0.05A-2A. Assemble 10 button batteries for each sample, test the battery performance under the same voltage and current, and take the average value.
- C2001B Wuhan Blue Electric Battery Test System
- Infrared spectra were measured on a Spectrum 100 (from Perkin Elmer) Fourier Transform Infrared Spectrometer using the potassium bromide pellet method. The test conditions included: the scanning range was from 500 cm -1 to 4000 cm -1 , and 32 scan signals were collected for each sample.
- the specific surface area was tested using ASAP2010 specific surface area and pore size distribution analyzer from Micromeritics, USA. Test conditions: temperature 77K, nitrogen atmosphere.
- Raman spectroscopy was performed using a laser with a wavelength of 785 nm as the excitation light source, using an Invia/Reflrx Laser Micro-Raman spectrometer, in which material samples were placed on glass slides for testing.
- the room temperature refers to 25°C.
- 4-bromoboronic acid diazobenzene tetrafluoroborate, tetrakis (triphenylphosphine) palladium [Pd(PPh 3 ) 4 ], triethylamine, cuprous iodide (CuI), 1,4-Diethynylbenzene, 4,4'-dibromotriphenylamine, N,N'-dimethylformamide (DMF) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.
- the raw graphene nanosheets were purchased from Changzhou Sixth Element Materials Technology Co., Ltd., and were few-layer graphene with a plane dimension of 2.0-5.0 ⁇ m.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 25mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 15 g graphene nanosheets (5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were sequentially treated with acetone , DMF and deionized water were rinsed once each, and dried in vacuum (drying temperature 60°C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-1;
- conjugated copolymer A-3 was prepared. The specific steps were as follows: 326 mg of 4,4'-dibromotriphenylamine, 138.6 mg of 1,4-diethynylbenzene, and 100 mL of N,N' were added. -In dimethylformamide, after stirring and dissolving, 35 mg of tetrakis(triphenylphosphine) palladium, 7 mg of cuprous iodide and 4 mL of triethylamine were added. The reaction mixture was heated to 80 °C under nitrogen protection and stirred for 72 h. After the reaction was completed, the reaction solution was poured into methanol, and the mixture was vacuum filtered to obtain a brown solid product.
- the obtained product was washed successively with methanol and deionized water for several times to remove unreacted monomers and catalysts, and dried in a vacuum oven (drying temperature was 60°C, drying time was 12h), and the product was conjugated copolymer A. -3.
- the specific surface areas of A-1, A-2 and A-3 were tested by the BET method by the test method as described above.
- the results show that the specific surface area of the pretreated graphene nanosheets A-1 is 420 m 2 /g, the specific surface area of the graphene conductive composite A-2 is 185 m 2 /g, and the surface area of the conjugated polymer A-3 is compared. is 5.5m 2 /g.
- the above results show that the surface morphology of graphene nanosheets changed after grafting the polymer. That is, the polymer coats the surface of the graphene nanosheets, thereby reducing the specific surface area of the graphene nanosheets themselves.
- FIG. 3 is the SEM of the graphene conductive composite A-2 obtained in Example 1.
- 4 is a SEM image of the raw graphene nanosheets in Example 1.
- Figure 5 is the SEM image of A-3. Comparing Fig. 3 and Fig. 4, it can be found that the surface of the grafted graphene nanosheets is smoother, and the stacking of sheets does not occur, while the stacking phenomenon is more obvious in the raw graphene nanosheets.
- Figure 5 also shows that when the conjugated copolymer is prepared in the absence of pretreated graphene nanosheets, the resulting conjugated copolymer can only form small spheres.
- the Raman spectrum of the graphene conductive composite material A-2 obtained in Example 1 was obtained.
- the results showed that the peak D was at 1354 cm -1 , the peak G was at 1574 cm -1 , and the peak height ratio ID / IG of the two was 0.09.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 35mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 15 g graphene nanosheets (5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were sequentially treated with acetone , DMF and deionized water were rinsed once each, and dried in vacuum (drying temperature 60°C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-4;
- the specific surface area of A-5 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-5 is 120 m 2 /g. Compared with Example 1, the grafting amount of the conjugated polymer in Example 2 is increased, which leads to a further decrease in the specific surface area of the graphene conductive composite.
- the Raman spectrum of the graphene conductive composite material A-5 obtained in Example 2 was obtained.
- the results show that the peak D is at 1354 cm -1 , the peak G is at 1580 cm -1 , and the peak height ratio ID / IG of the two is 0.07.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 12mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 15 g graphene nanosheets (5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were sequentially treated with acetone , DMF and deionized water were rinsed once each, vacuum dried (drying temperature 60 °C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-6;
- the specific surface area of A-7 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-7 is 144 m 2 /g.
- the Raman spectrum of the graphene conductive composite material A-7 obtained in Example 3 was obtained.
- the results show that the peak D is at 1354 cm -1 , the peak G is at 1580 cm -1 , and the peak height ratio ID / IG of the two is 0.07.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 25mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 10 g graphene nanosheets (5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were sequentially treated with acetone , DMF and deionized water were rinsed once each, and dried in vacuum (drying temperature 60°C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-8;
- the specific surface area of A-9 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-9 is 152 m 2 /g.
- the Raman spectrum of the graphene conductive composite material A-9 obtained in Example 4 was obtained.
- the results show that the peak D is at 1354 cm -1 , the peak G is at 1580 cm -1 , and the peak height ratio ID / IG of the two is 0.07.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 25mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 15 g graphene nanosheets (7.5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were successively treated with Rinse once with acetone, DMF and deionized water, and dry in vacuum (drying temperature 60°C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-10;
- the specific surface area of A-11 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-11 is 155 m 2 /g.
- the Raman spectrum of the graphene conductive composite material A-11 obtained in Example 5 was obtained.
- the results show that the peak D is at 1354 cm -1 , the peak G is at 1580 cm -1 , and the peak height ratio ID / IG of the two is 0.08.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 25mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 15 g graphene nanosheets (5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were sequentially treated with acetone , DMF and deionized water were rinsed once each, and dried in vacuum (drying temperature 60°C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-1;
- the specific surface area of A-12 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-12 is 160 m 2 /g.
- the Raman spectrum of the graphene conductive composite material A-12 obtained in Example 6 was obtained.
- the results showed that the peak D was at 1354 cm -1 , the peak G was at 1570 cm -1 , and the peak height ratio ID / IG was 0.15.
- solution A 25g of 4-bromoboronic acid diazobenzene tetrafluoroborate was dissolved in 25mL of water to obtain solution A. Under vigorous stirring, solution A was added dropwise to an aqueous dispersion of 15 g graphene nanosheets (5 g graphene nanosheets), then stirred at room temperature for 1 h, then poured into acetone, filtered to obtain solids, and the solids were sequentially treated with acetone , DMF and deionized water were rinsed once each, and dried in vacuum (drying temperature 60°C, drying time 4h) to obtain pretreated graphene nanosheets, denoted as A-1;
- the specific surface area of A-13 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-13 is 150 m 2 /g.
- the Raman spectrum of the graphene conductive composite material A-13 obtained in Example 7 was obtained.
- the results show that the peak D is at 1354 cm -1 , the peak G is at 1580 cm -1 , and the peak height ratio ID / IG of the two is 0.07.
- step (2) get the graphite after 10g pre-expanded in step (1), the Surfonic T-10 of 0.25g (purchased from Huntsman Chemical Trading Co., Ltd., is a kind of aliphatic amine polyoxyethylene ether, HLB value is 12.4), 239.75g of deionized water was added to the high-pressure homogenizer together, and homogenized for 30min under the pressure of 30MPa, and then the pressure was increased to homogenize under the pressure of 45MPa for 30min to obtain a slurry containing a stack of graphene nanosheets .
- the Surfonic T-10 of 0.25g purchasedd from Huntsman Chemical Trading Co., Ltd., is a kind of aliphatic amine polyoxyethylene ether, HLB value is 12.4
- 239.75g of deionized water was added to the high-pressure homogenizer together, and homogenized for 30min under the pressure of 30MPa, and then the pressure was increased to homogenize under the pressure of 45MPa for 30min to
- the above-mentioned slurry is dried by a spray drying device.
- the temperature of the air inlet is controlled to be 350°C
- the temperature of the air outlet is 100°C
- the rotational speed of the centrifugal disc of the sprayer is 20,000 rpm
- the powder collected at the outlet is the stack of graphene nanosheets.
- Example 1 Using the obtained graphene nanosheets to replace the raw material nanosheets, Example 1 was repeated to prepare the graphene conductive composite material A-14.
- the specific surface area of A-14 was tested by the BET method through the test method as described above. The results show that the specific surface area of the graphene conductive composite A-14 is 175 m 2 /g.
- the Raman spectrum of the obtained graphene conductive composite A-14 was obtained, and the results showed that the D peak was at 1355 cm -1 , the G peak was at 1580 cm -1 , and the peak height ratio ID/IG of the two was 0.05.
- reaction solution was poured into methanol, and the mixture was vacuum filtered to obtain a black solid. Subsequently, the resulting mixture was washed successively with methanol and deionized water for several times to remove unreacted monomers and catalysts, and dried in a vacuum oven (drying temperature was 60 °C, drying time was 12 h). The resulting mixture was added to toluene at 80°C and the solution was found to turn tan and black flocs were precipitated in the solution.
- the specific surface area of the product of Comparative Example 1 was tested by the BET method.
- the results show that the specific surface area of the product of Comparative Example 1 is 400 m 2 /g, which is basically the same as that of the raw graphene nanosheets, indicating that the polymer is not grafted on the surface of the graphene nanosheets.
- a negative electrode was prepared by using the graphene conductive composite material A-2 obtained in Example 1 as the conductive agent and the silicon carbon material as the active material. Specifically, 8g of silicon carbon material, 1g of A-2 conductive agent, and 1g of binder (polymethacrylic acid) were respectively added to a 50ml beaker, and stirred at a speed of 800rpm for 30min to obtain a negative electrode slurry. The above-mentioned negative electrode slurry was uniformly coated on copper foil by a coating machine (coating thickness: 100 ⁇ m), and dried overnight at 80° C. in a vacuum drying oven to obtain the negative electrode of the present invention. The SEM picture of the negative electrode was taken with a scanning electron microscope, and the result is shown in FIG. 6 .
- FIG. 6 and FIG. 7 are SEM images of the negative electrode of the present invention and the control negative electrode obtained in the application example 1 and application example 2, respectively.
- the graphene conductive composite material wraps the surface of the particles of the silicon carbon anode material. Without being bound by any theory, it is believed that this structure not only facilitates the formation of in-plane conduction of electrons, but also buffers the volume expansion of the silicon carbon material during charging and discharging, which may improve the cycling performance of the battery.
- Super P is dispersed among the particles of the silicon carbon anode material.
- the electron conduction mode is linear transport, and it does not contribute to alleviating the volume expansion of the silicon carbon material.
- FIG. 8 it is a rate cycle diagram of the batteries obtained in Application Example 1 and Application Example 2.
- FIG. 8 It can be seen from the figure that under the same cycle times, the capacity retention rate of the battery using the negative electrode of the present invention is higher.
- the negative electrode of the present invention uses the graphene conductive composite material A-2 as a conductive agent. This shows that A-2 can improve the conductivity of electrodes, inhibit the occurrence of battery polarization, and improve battery stability.
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Abstract
Description
Claims (11)
- 一种石墨烯导电复合材料,包括石墨烯纳米片和共轭共聚物,其中共轭共聚物含有炔基,呈线性结构,并与石墨烯纳米片接枝。
- 按照权利要求1所述的石墨烯导电复合材料,其特征在于,所述石墨烯导电复合材料的比表面积为50-300m 2/g,优选为100-250m 2/g,或所述石墨烯导电复合材料的拉曼光谱中具有D峰和G峰,其峰高分别为I D和I G,其中I D/I G在0.50以下。
- 按照权利要求1所述的石墨烯导电复合材料,其特征在于,以所述石墨烯导电复合材料的总质量为基准,所述石墨烯纳米片的质量含量为85%-99%,所述共轭共聚物的质量含量为1%-15%。
- 按照权利要求1-3任一所述的石墨烯导电复合材料,其特征在于,所述的石墨烯纳米片为少层石墨烯,优选少层石墨烯包含3-5层石墨烯;优选,所述石墨烯纳米片的平面维度尺寸为0.05-5.0μm。
- 按照权利要求1-4任一所述的石墨烯导电复合材料,其特征在于,所述的石墨烯纳米片的拉曼光谱中具有D峰和G峰,其峰高分别为I D和I G,其中I D/I G在0.50以下
- 按照权利要求1-5任一所述的石墨烯导电复合材料,其特征在于,所述共轭共聚物为聚芳炔共聚物、聚芴共聚物、聚对苯乙烯撑共聚物、聚对苯乙炔撑共聚物、聚噻吩共聚物、聚噻吩衍生物共聚物、聚吡咯共聚物、聚吡咯衍生物共聚物中的至少一种,优选所述共轭共聚物为聚芳炔共聚物、聚芴共聚物、聚噻吩共聚物以及聚噻吩衍生物共聚物中的至少一种,更优选所述共轭共聚物为1,4-二炔基苯-三苯胺共聚物,1,4-二炔基苯-9-己基芴共聚物,1,4-二炔基苯-3-己基噻吩共聚物,1,4-二炔基苯-噻吩共聚物,以及1,4-二炔基苯-3,4-乙烯二氧噻吩共聚物中的至少一种。
- 权利要求1-6任一所述石墨烯导电复合材料的制备方法,包括以下步骤:用4-溴硼酸重氮苯四氟硼酸盐对石墨烯纳米片进行预处理,以及 在预处理后的石墨烯纳米片存在下形成共轭共聚物。
- 按照权利要求7所述的方法,其特征在于,所述预处理包括:在搅拌下,将4-溴硼酸重氮苯四氟硼酸盐水溶液滴加到石墨烯纳米片的水分散液中,在-5℃-40℃的温度下处理30min-180min,反应产物经干燥,得到预处理后的石墨烯纳米片;优选地,所述4-溴硼酸重氮苯四氟硼酸盐水溶液的质量浓度为40%-70%;所述石墨烯纳米片的水分散液中石墨烯纳米片的质量浓度为5%-50%;优选地,所述的4-溴硼酸重氮苯四氟硼酸盐与石墨烯纳米片的质量比为3-6:1;优选地,所述的干燥采用真空干燥,其中干燥温度60-80℃,干燥时间为2-10h。
- 按照权利要求7所述的方法,其特征在于,所述在预处理后的石墨烯纳米片存在下形成共轭共聚物包括:在催化剂、溶剂以及预处理后的石墨烯纳米片存在下,使用于形成共轭共聚物的单体进行聚合反应,得到石墨烯导电复合材料;优选地,用于形成共轭共聚物的单体包括至少两种单体,其中第一单体含有卤素,第二单体为含炔基的化合物;优选地,所述催化剂选自钯催化剂、镍催化剂中的至少一种;优选地,聚合反应的条件如下:在惰性气氛下反应,反应温度80-150℃,反应时间12h-36h。
- 权利要求1-6任一所述石墨烯导电复合材料或权利要求7-9任一制备方法制得的石墨烯导电复合材料在锂离子电池中的应用。
- 一种锂离子电池,包括权利要求1-6任一所述石墨烯导电复合材料或权利要求7-9任一制备方法制得的石墨烯导电复合材料。
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