WO2024032649A1 - 一种激光诱导石墨烯及其制备方法 - Google Patents

一种激光诱导石墨烯及其制备方法 Download PDF

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WO2024032649A1
WO2024032649A1 PCT/CN2023/111931 CN2023111931W WO2024032649A1 WO 2024032649 A1 WO2024032649 A1 WO 2024032649A1 CN 2023111931 W CN2023111931 W CN 2023111931W WO 2024032649 A1 WO2024032649 A1 WO 2024032649A1
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graphene
laser
cellulose
lignin
lig
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PCT/CN2023/111931
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English (en)
French (fr)
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赵楠
解洪兴
何新
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北京亥素科技有限公司
柯灵爱尔(北京)环境技术中心
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Priority claimed from CN202210960048.1A external-priority patent/CN115072710B/zh
Priority claimed from CN202210960035.4A external-priority patent/CN115057433B/zh
Priority claimed from CN202210960536.2A external-priority patent/CN115141403B/zh
Priority claimed from CN202210942519.6A external-priority patent/CN115160627B/zh
Application filed by 北京亥素科技有限公司, 柯灵爱尔(北京)环境技术中心 filed Critical 北京亥素科技有限公司
Publication of WO2024032649A1 publication Critical patent/WO2024032649A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials

Definitions

  • the invention relates to the technical field of graphene materials, and in particular to a laser-induced graphene layered composite material and a production method thereof.
  • Graphene a single layer of graphite, is a two-dimensional crystal material with a single atomic layer of honeycomb structure formed by sp 2 hybridization of carbon atoms.
  • Graphene is an important member of the carbon nanomaterial family, which has shown broad application in electronic devices, energy storage, and electrochemical catalysis due to its unique physical properties, such as high surface area, high electrical conductivity, good mechanical strength, and stability. Application prospects.
  • the mechanical stripping method and the epitaxial growth method have low preparation efficiency and are difficult to meet large-scale needs.
  • the reduction of graphene oxide method is widely used, but most of the reducing agents used in its preparation process have shortcomings such as high toxicity and high pollution, which increases the cost of protection measures and waste liquid treatment during the preparation process.
  • the chemical vapor deposition method can obtain large-sized continuous graphene films, new impurities may be introduced during the peeling process, affecting the quality of graphene, and the reaction conditions are harsh and strict.
  • the above-mentioned common production methods also use graphite ore as raw materials.
  • This mineral resource is non-recyclable and is not conducive to the large-scale production of graphene. How to obtain high-quality, low-cost graphene through low-cost, large-scale, simple production steps, non-toxic and environmentally friendly preparation methods has become a research hotspot in this field.
  • Preparation of graphene by laser induction method is a new type of graphene preparation method. Its principle is to use laser induction to convert the precursor into graphene. This method can achieve low-cost preparation at room temperature and without a protective atmosphere.
  • Graphene material is used.
  • the inventor found that the laser-induced graphene (LIG) method is prone to cracks and unevenness when preparing laser-induced graphene (LIG).
  • the base material is prone to distortion and fracture, and the prepared LIG is not firmly bonded to the base material. Problems such as easy falling off.
  • the inventor provides a method for preparing a graphene layered composite material, which uses a laser to convert a substrate layer containing cellulose and a precursor into laser-induced graphene.
  • the inventor found through extensive research that during the process of laser-induced conversion, it is necessary to set the laser parameters reasonably so that the laser penetrates deep into the base material layer and converts the precursor into laser-induced graphene. At the same time, the laser does not damage the base material layer.
  • the lasers used in this preparation method include CO 2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the wavelength range of the laser that can be used can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, and 1053nm.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 .
  • the inventor also provides a graphene layered composite material, which includes a base material layer and a graphene functional layer.
  • the graphene functional layer contains laser-induced graphene components.
  • the graphene layered composite material contains cellulose, which is dispersed in the base material layer and the graphene functional layer.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; part of the cellulose and carbonized cellulose molecules are entangled with each other
  • a network structure is formed in which part of the laser-induced graphene components are nested.
  • graphene layered composite materials overcome the problem of unreliable bonding between the graphene functional layer and the base material layer, allowing the graphene and base material to be firmly bonded and not easy to fall off, and achieve excellent flexibility and weather resistance.
  • the inventor also provides a doped laser graphene material.
  • the graphene layered composite material includes a base material layer and a graphene functional layer.
  • the graphene functional layer contains laser-induced graphene.
  • the graphene functional layer also contains hybrids, which include iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, etc., and combinations of the above substances .
  • the graphene layered composite material contains cellulose, which is dispersed in the base material layer and the graphene functional layer.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; part of the cellulose and carbonized cellulose molecules are entangled with each other A network structure is formed in which part of the laser-induced graphene is nested.
  • graphene layered composite materials overcome the problem of unreliable bonding between the graphene functional layer and the base material layer, allowing the graphene and base material to be firmly bonded and not easy to fall off, and achieve excellent flexibility and weather resistance.
  • the graphene functional layer containing hybrids has excellent properties, such as high surface capacitance, high capacitance, low surface resistance, strong selectivity and other characteristics.
  • the inventor provides a method for preparing laser-doped graphene materials, which uses laser to convert a substrate layer containing cellulose and precursor into laser-induced graphene.
  • the inventor found through extensive research that doping substances such as iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, sulfur compounds, etc. are introduced into laser-induced graphite vinyl substrate.
  • the inventor also provides a method for preparing doped laser graphene materials. Cellulose is added to the LIG substrate, and during the laser-induced conversion process, the laser parameters are reasonably set to allow the laser to penetrate deeply into the LIG substrate.
  • the precursor is converted into laser-induced graphene, and part of the cellulose is converted into carbonized cellulose.
  • the laser does not destroy the bundle tube structure and network structure of carbonized cellulose, maintaining the stability of the graphene functional layer and the connection between the substrate layer and the laser. Induce the connection of graphene, so that the prepared induced graphene can better adhere to the surface of the substrate layer, solving the problem of unreliable combination between the graphene functional layer and the substrate layer, so that the graphene and the substrate can be firmly combined It is not easy to fall off and achieves excellent flexibility, weather resistance and other characteristics.
  • the properties of laser-induced graphene can be greatly improved, such as increasing surface capacitance, increasing capacitance, reducing surface resistance, enhancing selectivity and other properties.
  • the inventor provides a method for preparing a modified laser-induced graphene material, which uses a laser to convert a substrate layer containing cellulose and a precursor into laser-induced graphene.
  • the modification of the precursor includes oxidation, reduction, hydrolysis, alcoholysis, acidolysis of methoxy groups, carboxyl groups, photolysis, esterification, sulfonation, alkylation, halogenation, nitration, and polycondensation.
  • grafting, esterification, copolymerization and other chemical reactions can enhance the temperature resistance and carbon-forming properties of the precursor.
  • the flame retardant group is grafted onto the precursor to improve the high temperature resistance of the precursor.
  • the laser parameters need to be set appropriately so that the laser penetrates deep into the base material layer and converts the precursor into laser-induced graphene.
  • the laser does not destroy the cellulose in the base material layer and maintains
  • the stability of the base material layer and the connection between the base material layer and the laser-induced graphene make the prepared induced graphene better adhere to the surface of the base material layer and solve the problem of unreliable combination between the graphene functional layer and the base material layer.
  • the graphene and the substrate can be firmly combined and not easy to fall off, and achieve excellent flexibility, weather resistance and other characteristics.
  • the lasers used in this preparation method include CO 2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the wavelength range of the laser that can be used can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, and 1053nm.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 .
  • the inventor also provides a modified laser-induced graphene material.
  • the modified laser-induced graphene material includes a base material layer and a graphene functional layer.
  • the graphene functional layer contains laser-induced graphene components.
  • the base material layer also contains a modified precursor.
  • the modified precursor is connected/grafted with flame retardant groups.
  • the precursor can also be connected with epoxy groups and ester groups.
  • the modified laser-induced graphene material contains cellulose, and the cellulose is dispersed in the base material layer and the graphene functional layer.
  • the modified laser-induced graphene material In the structure of the modified laser-induced graphene material, part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; part of the cellulose and carbonized cellulose molecules are entangled with each other
  • the knots form a network structure in which some of the laser-induced graphene components are nested. Due to its special structure, the modified laser-induced graphene material overcomes the problem of unreliable bonding between the graphene functional layer and the base material layer, allowing the graphene and base material to be firmly bonded and not easy to fall off, and achieves excellent flexibility and weather resistance. sexual characteristics. Modified laser-induced graphene materials have modified precursors, so they have better temperature resistance, waterproofness, and flexibility.
  • the graphene layered composite material provided by the inventor can be used in flexible sensors, intelligent heating devices, nano-triboelectric generators, self-cleaning filters, supercapacitors and other fields.
  • Embodiment 1 A method for preparing a graphene layered composite material, wherein a laser is used to irradiate a LIG substrate to prepare a graphene layered composite material.
  • the wavelength range of the laser is 9.3-10.6 ⁇ m, 625-740 nm, 450- 480nm, 1053nm, the laser intensity range endured by the substrate surface is 3J/cm2-40J/ cm2 , the LIG substrate contains cellulose and precursor, and the thickness of the LIG substrate is 0.02-0.5mm.
  • Embodiment 2 The preparation method according to Embodiment 1, wherein the diameter of the cellulose is >100 nm and the aspect ratio is 1000-1500; or the diameter of the cellulose is 0.1-120um and the length is 0.5-5mm.
  • Embodiment 3 The preparation method according to Embodiment 1-2, wherein the precursor is lignin, and the particle size of the lignin is 10 nm-500 nm.
  • Embodiment 4 The preparation method according to embodiments 1-3, wherein the lignin addition amount is 0-41%.
  • Embodiment 5 The preparation method according to embodiments 1-4, wherein the added amount of lignin is 29%.
  • Embodiment 6 The preparation method according to embodiments 1-5, wherein the laser intensity range is 5.5-20J/cm 2 .
  • Embodiment 7 The preparation method according to embodiments 1-6, wherein the precursor includes biomass materials, synthetic materials, and mineral materials.
  • Embodiment 8 The preparation method according to embodiments 1-7, wherein the precursor is a biomass material, and the components of the biomass material include lignin, tannic acid, polyphenols, and flavonoids.
  • Embodiment 9 The preparation method according to embodiments 1-8, wherein the lignin includes Kraft lignin, alkali lignin, and dealkalized lignin.
  • Embodiment 10 The preparation method according to embodiments 1-9, wherein the synthetic materials include photoresist, polyimide film, polyimide fiber paper, polyimide foam sponge, and polysulfone polymer.
  • Materials Teflon, phenolic resin, ABS plastic, polystyrene polymer; mineral materials include coal, carbon black, graphene oxide, and graphite.
  • Embodiment 11 The preparation method according to embodiments 1-10, wherein the laser is generated by a laser, and the laser is one of a CO2 source laser, a blue light source, and a femtosecond laser.
  • Embodiment 12 The preparation method according to embodiments 1-11, wherein the power range of the laser is 0-50W.
  • Embodiment 13 The preparation method according to embodiments 1-12, wherein the LIG substrate is in an environment of protective gas, and the protective gas can be reducing and inert gas.
  • Embodiment 14 The preparation method according to embodiments 1-13, wherein the protective gas is H 2 , Ar, N 2 , SF 6 or a mixed gas of several gases.
  • the protective gas is H 2 , Ar, N 2 , SF 6 or a mixed gas of several gases.
  • Embodiment 15 A method for preparing layered laser-induced graphene substrate, including the following steps:
  • the precursor includes petroleum-based materials and bio-based materials
  • the petroleum and materials include graphene oxide and polyimide
  • the bio-based materials Materials include lignin, tea polyphenols, and tannins
  • the slurry is hot-pressed to form a LIG base material.
  • the thickness of the LIG base material is 0.02-0.5mm.
  • Embodiment 16 A method for preparing layered laser-induced graphene substrate, including the following steps:
  • the adhesion liquid contains precursors.
  • the precursors include petroleum-based materials and bio-based materials.
  • the petroleum and materials include graphene oxide and polyimide.
  • the bio-based materials include lignin, tea. Polyphenols, tannins;
  • the LIG base material contains cellulose.
  • the attachment method can be dipping, coating, or spraying;
  • Embodiment 17 The preparation method according to embodiments 1-16, wherein the mixing method includes stirring, ultrasonic, and emulsification; the preparation method further includes using a casting method or a vacuum filtration method to add cellulose-reinforced
  • the raw materials are prepared into a cellulose-reinforced base material slurry wet film; the base material slurry wet film is solidified into a cellulose-reinforced thin-layer base material using a hot pressing forming method.
  • Embodiment 18 The preparation method according to embodiments 1-17, wherein the temperature of hot press molding is 40-150°C and the pressure is 1-15MPa.
  • Embodiment 19 The preparation method according to embodiments 1-18, wherein the temperature of hot press molding is 50-100°C and the pressure is 5-10MPa.
  • a certain amount of cellulose is added to the LIG base material, and the power and wavelength of the laser are controlled at the same time, so that part of the cellulose entering the graphene functional layer is converted into carbonized Cellulose, and part of the cellulose and carbonized cellulose molecules are entangled with each other to form a network structure, and some laser-induced graphene components are nested in the network structure.
  • These celluloses will more firmly connect the base material layer and the graphene functional layer, overcoming the problem of unreliable bonding between the graphene functional layer and the base material layer, allowing graphene and the base material to be firmly bonded and not easy to fall off, and achieve excellent results. Flexibility, weather resistance and other characteristics.
  • the precursor can better wrap the cellulose, protect the cellulose from being carbonized during the laser scanning process, and maintain the bundle tube structure of the cellulose. stability, so that the final generated laser-induced graphene can better adhere to the surface of the substrate layer.
  • FIG. 8 Schematic diagram of the roll-to-roll LIG preparation process
  • FIG. 10 Schematic diagram of graphene layered composite material containing cellulose
  • FIG 11 SEM images of pure cellulose paper (left), lignocellulose composite paper (middle) and LIG prepared based on lignocellulose composite paper (right)
  • Figure 12 SEM images of lignocellulose LIG substrate (left), 1 scan of lignocellulose LIG substrate (middle), and 2 scans of lignocellulose LIG substrate (right)
  • FIG. 13 Schematic diagram of the process of preparing LIG based on lignocellulose LIG substrate
  • FIG 14 SEM images of LIG prepared based on lignocellulosic LIG substrate (different laser intensities, (a) 50wt%, (b) 60wt%, (c) 70wt%, (d) 80wt%, full power is 40W)
  • FIG 16 TEM images of LIG prepared based on lignocellulose LIG substrate (different lignin addition amounts, (a, b) 2wt%, (c, d) 9wt%, (e, f) 15wt%, (g, h)21wt%,(i,j)34wt%)
  • FIG. 17 Schematic diagram of laser-induced graphene nested in cellulose and carbonized cellulose structures
  • Figure 18 is a schematic structural diagram of the supercapacitor in the embodiment.
  • Figure 20 is a schematic structural diagram of the Joule heater in the embodiment.
  • Figure 21 is a schematic structural diagram of the gas sensor in the embodiment.
  • FIG. 22 Schematic diagram of the appearance of the graphene supercapacitor in the embodiment
  • FIG. 23 Schematic diagram of a supercapacitor containing two layers of graphene composite material in the embodiment
  • Figure 25 is a schematic structural diagram of the graphene supercapacitor in the embodiment.
  • Figure 26 is a schematic structural diagram of the internal parallel graphene supercapacitor provided in the embodiment.
  • Figure 27 is a schematic diagram of the preparation process of a graphene strain sensor provided in the embodiment.
  • Figure 28 is a schematic structural diagram of a graphene strain sensor provided in the embodiment.
  • Figure 29 is a schematic diagram of the composition and structure of a graphene gas sensor provided in the embodiment.
  • Figure 30 is a schematic flow diagram of an applied gas detection principle provided in the embodiment.
  • Figure 31 Schematic diagram of potential roll-to-roll LIG electrode manufacturing process based on pulping, papermaking and laser scribing processes
  • FIG 32 Schematic diagram of the epoxidation and acrylation process of lignin
  • Figure 33 Schematic diagram of the multilayer structure formed by FeNi 3 nanoparticles and their oxide (Fe 3 O 4 ) in the LIG matrix.
  • Figure 34 Schematic diagram showing the structure of nitrogen-doped laser-induced graphene.
  • Graphene is a new material in which carbon atoms connected by sp 2 hybridization are closely packed into a single-layer two-dimensional honeycomb lattice structure.
  • Laser-induced graphene is a new porous material with a three-dimensional honeycomb lattice structure in which carbon atoms connected by sp 2 hybridization are closely packed into multiple layers (usually more than five layers).
  • the precursor also called LIG precursor, is the precursor material for generating laser-induced graphene.
  • Cellulose layered materials prepared from cellulose or nanocellulose, or mixtures thereof
  • Laser-induced graphene substrate also called LIG substrate, is a substrate used to prepare laser-induced graphene by laser method.
  • Doping substances Iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, sulfur compounds, etc. can be introduced into the laser-induced graphene base material to enhance the laser Substances that induce properties related to graphene materials.
  • Hybrid refers to a substance (containing functional groups) generated after laser scanning after adding one kind of doping substance or its combination to the LIG substrate.
  • One embodiment of the present invention provides a flexible graphene composite material, which includes a base material layer and a graphene functional layer.
  • the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the base material layer contains cellulose, and also contains one or more other precursors that are easily induced by laser graphitization, such as bio-based materials, including paper and textiles.
  • the textiles can be silk, cotton and linen, etc.; synthetic materials, Including photoresist, polyimide (PI), PI fiber paper, PI foam sponge, polysulfone polymers (such as PES, etc.), Teflon (such as PTFE, FEP, PFA, ETFE), phenolic resin, ABS Plastics, polystyrene polymers, etc.; mineral materials, including coal, carbon black, graphene oxide (GO), and graphite.
  • PI polyimide
  • PI fiber paper such as PES, etc.
  • Teflon such as PTFE, FEP, PFA, ETFE
  • mineral materials including coal, carbon black, graphene oxide (GO), and graphite.
  • the proportion of precursor in the base material layer is 2wt%-40wt%, and the preferred proportion is 10wt%-30wt%.
  • the precursor type in the base layer can be a bio-based material, and the preferred bio-based material is lignin, and the particle size of lignin is 10 nm-500 nm.
  • the diameter of cellulose in the base layer is >1000nm, and the TEM results of different lignin addition amounts are shown in Figure 16.
  • the production method of laser-induced graphene is to use laser irradiation of a carbon-containing precursor to generate a local instantaneous high temperature (>1000°C) on the surface of the precursor, allowing the carbon atoms to complete the hybridization from sp 3 to sp 2 , forming a honeycomb-like structure. Structure of 3D porous graphene.
  • the cellulose in the precursor can be graphitized under laser irradiation of appropriate intensity without being destroyed and decomposed by high temperature. This will form carbonized cellulose and maintain the unique bundle tube structure of cellulose. Cellulose (including carbonized cellulose) ) can still maintain the mesh skeleton structure after laser scanning.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated laser induces better adhesion of graphene to the surface of the substrate layer. If the amount of precursor added is too low, the carbon source layer covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • One embodiment of the present invention provides a method for preparing a graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG base material to prepare a graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the base material layer includes a precursor.
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the precursor particle size is 10nm-500nm. Cellulose diameter>1000nm.
  • the preferred precursor can be lignin, graphene oxide, or polyimide.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules interact with each other.
  • the tangles form a network in which some of the laser-induced graphene is nested.
  • the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested.
  • the base material layer includes a precursor, and the precursor may be a biomass material, including paper, textiles, and the textiles may be silk, cotton, linen, etc.
  • Biomass materials include lignin (Kraft lignin, alkali lignin, dealkalized lignin, etc.), cellulose, tannic acid, polyphenols (such as tea polyphenols, chlorogenic acid, apple polyphenols, cocoa polyphenols) , resveratrol, etc.), flavonoids (such as flavonols, anthocyanins, flavonoids, etc.).
  • the use of biomass materials has many advantages such as environmental friendliness and degradability.
  • the particle size of lignin can be at the nanometer level, such as nano-lignin particles, with a particle size range of 50-500nm, which can be used as a better pore filler to occupy the middle nanometer level. pores.
  • One embodiment of the present invention provides a method for preparing a modified laser-induced graphene substrate. The specific steps include:
  • Precursor modification, modification of precursor includes oxidation, reduction, hydrolysis, alcoholysis, acidolysis of methoxyl group, carboxyl group, photolysis, esterification, sulfonation, alkylation, halogenation, nitration, Various chemical reactions such as polycondensation, grafting, esterification, and copolymerization enhance the temperature resistance and carbon-forming properties of the precursor. Modification mainly occurs on the phenolic hydroxyl groups in the precursor. Further precursors are connected with epoxy groups and ester groups.
  • the precursor is grafted and esterified, and the epoxy group is grafted onto the phenolic hydroxyl group of the precursor through a chemical catalysis method, and then an esterification reaction occurs with acrylic acid to prepare epoxy.
  • Precursor acrylate solution to improve precursor viscosity and castability at high temperatures.
  • Preparation of a precursor and cellulose mixed solution Add cellulose or nanocellulose to the precursor solution, stir, ultrasonic, and emulsify to prepare a precursor cellulose mixed solution.
  • the amount of precursor added is 0-41wt%, and the preferred amount of precursor added is 29wt%.
  • the amount of modified precursor/cellulose added, the amount of modified precursor added: 0-34wt%, the preferred amount of modified precursor added is 21wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the precursor cellulose wet film is solidified into a film at 40-150°C, 1-15MPa to become the precursor cellulose LIG substrate.
  • the preferred temperature is 50-110°C, and the preferred pressure is 5 -10MPa.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the quality of the laser-induced graphene prepared by it can be improved, such as improving the conductivity and hydrophobicity of the laser-induced graphene.
  • the strength and flexibility of the LIG substrate can also be improved.
  • One embodiment of the present invention provides a method for preparing doped graphene materials.
  • the method uses a laser-induced method to convert a LIG substrate into laser-induced graphene.
  • the LIG substrate can be doped, such as doped with iron.
  • Specific implementation methods include:
  • LIG substrate contains cellulose.
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • Optional doping substances include iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, sulfur compounds, etc.
  • Iron-based element compounds include ferric chloride, ferric nitrate, nickel chloride, nickel nitrate, cobalt chloride, and cobalt nitrate;
  • manganese compounds include manganese oxide; nitrogen compounds include urea and melamine;
  • boron compounds include boric acid and borate; phosphorus compounds Including phosphoric acid and phosphate; gold compounds include tetrachloroauric acid and potassium cyanoaurate; silver compounds include silver oxide, silver hydroxide, silver sulfide, silver sulfate, silver halide, and silver nitrate.
  • the doping method can be to directly mix doping substances into the LIG substrate raw materials, or to attach these doping substances to the surface of the LIG substrate through spraying, dipping, deposition,
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • Laser-induced graphene doped with iron-based element compounds and manganese compounds can be used as electrodes for supercapacitors. During the process of storing electricity in such electrodes, these doped iron-based element compounds and manganese compounds will undergo chemical reactions, making the capacitor Form pseudocapacitance and increase the capacitance of supercapacitor.
  • Laser-induced graphene doped with gold compounds, silver compounds, gold elements, and silver elements serve as conductive agents and can directly reduce the resistance of laser-induced graphene.
  • One embodiment of the present invention provides a flexible graphene composite material, which includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure. In the structure of graphene layered composites, part of the laser-induced graphene is nested in the network structure.
  • the ratio of graphene in the graphene functional layer to laser-induced graphene is 1:1-1:2.
  • I G / ID is 0.5- 5.0
  • I 2D /I G is 0.1-1.0
  • L a is 10-40mm.
  • the surface resistance of the graphene functional layer is 2-33000 ⁇ /square, and ⁇ /square is the same as ⁇ /cm 2 .
  • the conductivity of the graphene functional layer is 8-5500S/cm.
  • the specific surface area of the graphene functional layer is 10-350m 2 /g.
  • the pore diameter of the graphene functional layer is 0-750nm.
  • the thickness of the graphene functional layer is 0.05-350 ⁇ m.
  • the detection method of the ratio of graphene to laser-induced graphene is TEM detection.
  • the thickness of the base material layer is 0.02-0.5mm.
  • One embodiment of the present invention provides a flexible graphene composite material, which includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested.
  • the ratio of graphene to laser-induced graphene in the graphene functional layer is 1:1-1:2, and the detection method of the ratio of graphene to laser-induced graphene is TEM detection.
  • I G / ID is 1.0-3.3
  • I 2D /I G is 0.4-0.8
  • L a is 20-45mm.
  • the surface resistance of the graphene functional layer is 18-150 ⁇ /square.
  • the conductivity of the graphene functional layer is 50-200S/cm.
  • the specific surface area of the graphene functional layer is 10-350m 2 /g.
  • the pore diameter of the graphene functional layer is 0-750nm.
  • the thickness of the graphene functional layer is 0.05-35 ⁇ m.
  • the relative content of C of the graphene functional layer is 85wt%-93wt%
  • the relative content of O is 5wt%-10wt%
  • the relative content of N is 2wt%-5wt%, as shown in Figures 3 to 7.
  • the base material layer may be cellulose-reinforced polyimide, where the mass ratio of cellulose to polyimide is 4:1.
  • Cellulose forms an intertwined network structure in the base material layer, and polyimide adheres to the fiber surface of cellulose.
  • the liquid polyimide can also penetrate into the fiber surface of cellulose.
  • cellulose-reinforced polyimide fiber paper has larger free space/pores than polyimide membranes.
  • the air permeability of the polyimide fiber paper base material layer is 1700-2200mL ⁇ mm ⁇ (cm 2 ⁇ h ⁇ mmAq) -1 .
  • Tensile index of polyimide fiber paper >40N ⁇ m/g
  • tear index >30mM ⁇ m 2 /g
  • electrical constant 1.5-2.0
  • dielectric loss factor 3.1 ⁇ 10 -3 -6.5 ⁇ 10 -3 .
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested.
  • Substrates include lignin and cellulose.
  • I G / ID is 0.5-3.4
  • I 2D /I G is 0.2-0.8
  • L a is 10-40 mm.
  • the base material layer is lignocellulose blend composite paper: the tensile strength is 30-130MPa, and the contact angle is 30-80°.
  • the base material layer is lignin nanocellulose blend composite paper: tensile strength 50-250MPa, contact angle 50-90°.
  • the I G /I D of laser-induced graphene of lignin nanocellulose blend composite paper is 0.5-3.0, I 2D /I G 0.1-0.8, L a 25-150mm, and the surface resistance is 5-50 ⁇ /square.
  • nanocellulose can enhance the mechanical strength and surface hydrophobicity of composite paper.
  • the surface of the composite paper formed is smoother, with smaller porosity and Most of them are micropores, making it difficult for lasers to penetrate, and energy (heat) cannot be evenly and effectively conducted to the inside of the composite paper, which will hinder the graphitization of lignin, resulting in high energy consumption and high resistance of the LIG formed.
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested.
  • Substrates include lignin and cellulose.
  • the base material layer is heat-pressed at 100MPa and 100°C.
  • the base material layer is scanned by laser.
  • the laser scanning speed is 175mm/s
  • the laser intensity is 32W
  • the laser focal length is 0, that is, it is focused on the surface of the base material layer.
  • the diameter of cellulose in the base material layer is 15-30um
  • the particle size of lignin is >500nm. As shown in Figure 1 to Figure 2.
  • Table 1 contains cellulose and lignin substrate layers and LIG parameters
  • Nanocellulose can enhance the mechanical strength and surface hydrophobicity of composite paper.
  • the surface of the composite paper formed is smoother, with smaller porosity and mostly micropores, resulting in laser It is difficult to penetrate, and energy (heat) cannot be conducted evenly and effectively into the interior of the composite paper, which will hinder the graphitization of lignin, resulting in high energy consumption and high resistance of the formed LIG.
  • the diameter of the cellulose also affects the mechanical strength of the substrate layer, as well as the waterproofing properties (contact angle).
  • the cellulose added to the base material layer is nanocellulose, the diameter of nanocellulose is ⁇ 100nm, and the particle size of lignin is >500nm.
  • the base material layer has been heat-pressed at 100MPa and 100°C. Its mechanical tensile strength and contact angle are as follows.
  • Adding nanocellulose to the base material layer can enhance the mechanical tensile strength of the base material layer and improve the hydrophobic properties of the base material layer.
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the substrate layer includes cellulose and nanolignin. Nano-lignin can significantly improve the quality of laser-induced graphene. At the same time, the smaller the particle size of nano-lignin, the better the quality of laser-induced graphene.
  • Nano-lignin can better coat the surface of cellulose and protect the nano-cellulose from being decomposed during laser irradiation. At the same time, nanolignin is converted into laser-induced graphene. Thereby improving the quality of the graphene functional layer.
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • Different diameters of cellulose in the substrate layer have an impact on the quality of laser-induced graphene.
  • the inventor found through extensive research that the quality of laser-induced graphene prepared by adding ordinary cellulose to the base material layer is better than that of laser-induced graphene prepared by adding nanocellulose into the base material layer. Therefore, ordinary cellulose can be used as an additive to enhance the substrate layer, improving the quality of laser-induced graphene and reducing costs at the same time.
  • Table 4 contains parameters of different cellulose diameters and nano-lignin substrate layers
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • a substrate layer includes cellulose and tannic acid.
  • the base material layer is heat-pressed at 100MPa and 100°C.
  • the base material layer is scanned by laser.
  • the laser scanning speed is 175mm/s, the laser intensity is 32W, and the laser focal length is 0, that is, it is focused on the surface of the base material layer.
  • the performance parameters of the base material layer and graphene functional layer are as follows.
  • Table 5 contains cellulose and tannic acid substrate layer parameters
  • a base material layer includes cellulose and tea polyphenols.
  • the base material layer is heat-pressed at 100MPa and 100°C.
  • the base material layer is scanned by laser.
  • the laser scanning speed is 175mm/s, the laser intensity is 32W, and the laser focal length is 0, that is, it is focused on the surface of the base material layer.
  • the performance parameters of the base material layer and graphene functional layer are as follows.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested.
  • One embodiment of the present invention provides a doped laser graphene material, which includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure. In the structure of graphene layered composites, part of the laser-induced graphene is nested in the network structure.
  • the graphene functional layer also contains hybrids, which include iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, etc., and combinations of the above substances .
  • the ratio of graphene in the graphene functional layer to laser-induced graphene is 1:1-1:2.
  • I G / ID is 0.5- 5.0
  • I 2D /I G is 0.1-1.0
  • L a is 10-40mm.
  • the surface resistance of the graphene functional layer is 2-33000 ⁇ /square, and ⁇ /square is the same as ⁇ /cm 2 .
  • the conductivity of the graphene functional layer is 8-5500S/cm.
  • the specific surface area of the graphene functional layer is 10-350m 2 /g.
  • the pore diameter of the graphene functional layer is 0-750nm.
  • the thickness of the graphene functional layer is 0.05-350 ⁇ m.
  • the detection method of the ratio of graphene to laser-induced graphene is TEM detection.
  • the thickness of the base material layer is 0.02-0.5mm.
  • One embodiment of the present invention provides a modified laser-induced graphene material, which includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure. In the structure of the modified laser-induced graphene material, part of the laser-induced graphene is nested in the network structure.
  • the base material layer also contains a modified precursor, and the further modified precursor is connected/grafted with a flame retardant group.
  • the flame retardant group includes a halogen group and a phosphorus group. Further precursors are connected with epoxy groups and ester groups.
  • the ratio of graphene in the graphene functional layer to laser-induced graphene is 1:1-1:2.
  • I G / ID is 0.5- 5.0
  • I 2D /I G is 0.1-1.0
  • L a is 10-40mm.
  • the surface resistance of the graphene functional layer is 2-33000 ⁇ /square, and ⁇ /square is the same as ⁇ /cm 2 .
  • the conductivity of the graphene functional layer is 8-5500S/cm.
  • the specific surface area of the graphene functional layer is 10-350m 2 /g.
  • the pore diameter of the graphene functional layer is 0-750nm.
  • the thickness of the graphene functional layer is 0.05-350 ⁇ m.
  • the detection method of the ratio of graphene to laser-induced graphene is TEM detection.
  • the thickness of the base material layer is 0.02-0.5mm.
  • One embodiment of the present invention provides a mechanical sensor using graphene layered composite material.
  • the mechanical sensor is deformed under the action of external force, which will indirectly change the distribution and contact state of the internal LIG material, thereby causing regular changes in LIG resistance. , can be used to detect changes in electrical signals of tension and pressure.
  • Mechanical sensors based on graphene layered composite materials include graphene electrodes, graphene interdigital electrodes, and plastic sealing films.
  • the mechanical sensor of graphene layered composite material includes LIG disc electrode based on PI fiber membrane, LIG interdigital electrode based on kraft paper, and plastic sealing film.
  • Mechanical sensors of graphene layered composite materials can be used to monitor human body status in real time, such as human body pressure distribution display, pillow pressure distribution, sleeping posture monitoring and judgment, sitting posture monitoring and judgment, foot pressure and other directions. Its output resistance or voltage increases as the sensor strain increases. Through a specific strain-resistance/voltage relationship and combined with related algorithms, it can be widely used in different fields such as smart wearable devices, human-computer interaction, and medical rehabilitation.
  • One embodiment of the present invention provides a sensor system using graphene layered composite material, including a signal amplifier, an LCR functional microcontroller, and a Bluetooth communication module. After the sensor senses the mechanical change, it transmits the corresponding electrical signal to the signal amplifier. After the signal is amplified, it is transmitted to the microcontroller. The microcontroller collects, processes and reads the data, and then transmits it to the mobile phone through Bluetooth communication mode. Perform data point plotting and presentation.
  • One embodiment of the present invention provides a sensor material for an electrochemical sensor using graphene layered composite material.
  • Graphene works by reacting with the object being measured and generating an electrical signal proportional to the concentration of the reactant. It can be used for detection of humidity, temperature, gas, liquid, chemical substances, etc.
  • An embodiment of the present invention provides an electrode material of a supercapacitor and a supercapacitor.
  • the electrode material contains bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure. In the structure of the graphene layered composite material, part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested. Laser-induced graphene is used to store charges, which can improve the energy density and cycle life of supercapacitors and reduce manufacturing costs.
  • One embodiment of the present invention provides a method for preparing a graphene composite material.
  • the method uses a laser to convert a LIG substrate containing cellulose into graphene, as shown in Figure 11.
  • the specific implementation is to set the laser processing parameters and irradiate the surface of the LIG substrate with laser to convert the precursor into graphene.
  • the wavelength of the laser may be 9.3-10.6 ⁇ m, 625-740 nm, 450-480 nm, or 1053 nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the substrate can be utilized, as shown in Figure 12.
  • the LIG substrate contains cellulose components.
  • the LIG substrate contains a precursor, which can be a biomass material, including paper, textiles, and the textiles can be silk, cotton, linen, etc.
  • Biomass materials include lignin (Kraft lignin, alkali lignin, dealkalized lignin, etc.), cellulose, tannic acid, polyphenols (such as tea polyphenols, chlorogenic acid, apple polyphenols, cocoa polyphenols) , resveratrol, etc.), flavonoids (such as flavonols, anthocyanins, flavonoids, etc.).
  • lignin Kelraft lignin, alkali lignin, dealkalized lignin, etc.
  • cellulose cellulose
  • tannic acid such as tea polyphenols, chlorogenic acid, apple polyphenols, cocoa polyphenols
  • flavonoids such as flavonols, anthocyanins, flavonoids, etc.
  • the use of biomass materials has many advantages such as environmental friendlines
  • Cellulose is a semi-rigid molecule with flexible molecular chains, high degree of cellulose polymerization, good molecular orientation, and strong chemical stability. Adding cellulose to the LIG base material can take advantage of the advantages of cellulose as a semi-rigid molecule to form a network structure in the composite system, making the LIG base material have larger free space/pores. When the laser beam irradiates the surface of the LIG substrate, it is easier to penetrate deep into the paper, allowing the paper to absorb more heat and distribute the heat more evenly.
  • the unique pore structure of cellulose can guide graphene to better fill the free space of the paper when it grows on the surface of the paper, and evenly distribute on the surface of the paper, instead of growing vertically downward (distributed in a disorderly manner).
  • the surface of the graphene functional layer formed at this time is smoother and flatter with fewer cracks.
  • the substrate under laser scanning, the substrate is easily distorted or even broken due to the influence of high temperature, causing the graphene functional layer to easily fall off from the substrate; in contrast, due to the polarity of cellulose molecules, the molecular chains interact with each other.
  • the force is very strong and is not prone to severe shape distortion. It can firmly grasp the graphene growing on the surface of the paper and improve the overall mechanical stability of the graphene composite.
  • the TEM images of different lignin addition amounts are shown in Figure 16.
  • One embodiment of the present invention provides a method for preparing a graphene composite material, which converts a LIG substrate containing cellulose into graphene using a laser. Specific steps include:
  • the lignin purification method includes the following steps:
  • the lignocellulose wet film is cured into a film at 40-150°C, 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C, and the preferred pressure is 5-10MPa.
  • the lignocellulose LIG substrate is irradiated with laser to generate a graphene functional layer on the surface of the lignocellulose LIG substrate.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the substrate surface needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the substrate can be utilized, as shown in Figure 12.
  • the base material contains cellulose components.
  • Nanocellulose can enhance the mechanical strength and surface hydrophobicity of composite paper.
  • the surface of the composite paper formed is smoother, with smaller porosity and mostly micropores, resulting in laser It is difficult to penetrate, and energy (heat) cannot be conducted evenly and effectively into the interior of the composite paper, which will hinder the graphitization of lignin, resulting in high energy consumption and high resistance of the formed LIG.
  • Adding nanocellulose to the base material layer can enhance the mechanical tensile strength of the base material layer and improve the hydrophobic properties of the base material layer.
  • Nano-lignin can better coat the surface of cellulose and protect the nano-cellulose from being decomposed during laser irradiation. At the same time, nanolignin is converted into laser-induced graphene. Thereby improving the quality of the graphene functional layer.
  • lignin is a rigid macromolecule, it has high hardness but is slightly brittle; while cellulose is a semi-rigid molecule. Although its strength is poor, its molecular chain flexibility is better than that of lignin, and cellulose has a high degree of polymerization and molecular orientation. Good strength and strong chemical stability. Adding cellulose to lignin can combine the advantages of both (hardness and flexibility) to form a network structure in the composite system, making the lignin composite paper have larger free space/pores. When the laser beam irradiates the surface of the composite paper, it is easier to penetrate deep into the paper, allowing the paper to absorb more heat and distribute the heat more evenly.
  • the unique pore structure of cellulose can guide graphene to better fill the free space of the paper when it grows on the surface of the paper, and evenly distribute on the surface of the paper, instead of growing vertically downward (distributed in a disorderly manner).
  • the LIG surface formed at this time is smoother and flatter with fewer cracks.
  • lignin is easily distorted or even broken due to the influence of high temperature, causing laser-induced graphene to easily fall off from the substrate layer; in contrast, due to the polarity of cellulose molecules, the molecular chains are The interaction force is very strong and is not prone to severe shape distortion. It can firmly grasp the graphene grown on the surface of the paper and improve the overall mechanical stability of the graphene composite material.
  • One embodiment of the present invention provides a method for preparing a graphene composite material, which converts a LIG substrate containing cellulose into graphene using a laser. Specific steps include:
  • the lignin purification method includes the following steps:
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add conventional cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C and the preferred pressure is 5 -10MPa.
  • the lignocellulose LIG substrate is irradiated with laser to generate laser-induced graphene on the surface of the lignocellulose LIG substrate.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the substrate surface needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the substrate can be utilized.
  • the base material contains cellulose components.
  • Adding conventional cellulose to the LIG base material that is, cellulose with larger diameter and length, makes the conventional cellulose fibers thicker and creates larger pores in the LIG base material, which can better allow the laser to penetrate deeper into the LIG.
  • a higher quality LIG is formed with lower sheet resistance.
  • Adding nanocellulose, that is, smaller cellulose, to the LIG base material can make the graphene composite material denser and improve its tensile strength, waterproof performance, etc.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • LIG substrate preparation the method includes the following steps:
  • the LIG base material contains cellulose; the lignin mass percentage of the lignin solution is 2wt%-25wt%.
  • the curing temperature is 40-150°C, 1-15MPa; the preferred temperature is 50-100°C, and the preferred pressure is 5-10MPa.
  • the LIG substrate impregnated with lignin is irradiated with laser to generate laser-induced graphene on the surface of the LIG substrate.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the substrate surface needs to be >3J/cm 2 , and the preferred laser intensity is 8-50J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • lignin is a rigid macromolecule, it has high hardness but is slightly brittle; while cellulose is a semi-rigid molecule. Although its strength is poor, its molecular chain flexibility is better than that of lignin, and cellulose has a high degree of polymerization and molecular orientation. Good strength and strong chemical stability. Introducing lignin into a cellulose-containing substrate can combine the advantages of both (hardness and flexibility) to form a network structure in the composite system, allowing the substrate to have larger free space/pores. When the laser beam irradiates the surface of the LIG substrate, it is easier to penetrate deep into the paper, causing the LIG substrate to absorb more heat and distribute the heat more evenly.
  • the unique pore structure of cellulose can guide graphene to better fill the free space of the paper when it grows on the surface of the paper, and evenly distribute on the surface of the paper, instead of growing vertically downward (distributed in a disorderly manner).
  • the surface of the graphene functional layer formed at this time is smoother and flatter with fewer cracks.
  • lignin is easily distorted or even broken due to the influence of high temperature, causing laser-induced graphene to easily fall off; in contrast, due to the polarity of cellulose molecules, the interaction between molecular chains is very strong. , is not prone to serious shape distortion, can firmly grasp the graphene grown on the surface of the paper, and improves the overall mechanical stability of the graphene composite material.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • Lignin modification Modification of lignin includes oxidation, reduction, hydrolysis, alcoholysis, acidolysis of methoxyl group, carboxyl group, photolysis, phthalation, sulfonation, alkylation, halogenation, nitration, Various chemical reactions such as polycondensation, grafting, esterification, and copolymerization enhance the resistance and char-forming properties of lignin.
  • the lignin is grafted and esterified, and the epoxy group is grafted onto the phenolic hydroxyl group of the lignin through a chemical catalysis method, and then esterified with acrylic acid to prepare epoxy.
  • Lignin acrylate solution to improve lignin's stickiness and castability at high temperatures.
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-110°C and the preferred pressure is 5 -10MPa.
  • the lignocellulose LIG substrate is irradiated with laser light to convert the precursor in the lignocellulose LIG substrate into graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • the power range of the laser is 5-30W, and the irradiation power can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate containing the cellulose component can be utilized.
  • One embodiment of the present invention provides a method for preparing a modified laser-induced graphene substrate. The specific steps include:
  • flame retardant groups are grafted onto the precursor.
  • the flame retardant groups include halogen groups and phosphorus groups.
  • the mass ratio of the flame retardant group material to the precursor is 0-10wt%, and the mass ratio of the further flame retardant group material to the precursor is 3-8wt%.
  • Preparation of a precursor and cellulose mixed solution Add cellulose or nanocellulose to the precursor solution, stir, ultrasonic, and emulsify to prepare a precursor cellulose mixed solution.
  • the amount of precursor added is 0-41wt%, and the preferred amount of precursor added is 29wt%.
  • the amount of modified precursor/cellulose added, the amount of modified precursor added: 0-34wt%, the preferred amount of modified precursor added is 21wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the precursors can be lignin, tannic acid, tea polyphenols, etc.
  • the precursor cellulose wet film is solidified into a film at 40-150°C, 1-15MPa to become the precursor cellulose LIG substrate.
  • the preferred temperature is 50-110°C, and the preferred pressure is 5 -10MPa.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the quality of the laser-induced graphene prepared by it can be improved, such as improving the conductivity and hydrophobicity of the laser-induced graphene.
  • the strength and flexibility of the LIG substrate can also be improved.
  • One embodiment of the present invention provides a method for preparing a modified laser-induced graphene substrate.
  • the laser graphene precursor is lignin.
  • the specific steps include:
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin to obtain organic solvent-soluble lignin.
  • organic solvent extraction and classification Through organic solvent extraction and classification, the molecular weight and particle size of lignin can be controlled, non-functional components can be removed, the relative content of active groups can be increased, and the processability of lignin can be enhanced.
  • ethanol or butanol-soluble lignin can also be extracted using ethanol or butanol.
  • Modification of lignin includes grafting and esterification reactions to enhance the temperature resistance and carbon-forming properties of lignin.
  • the lignin is grafted and esterified, and the epoxy group is grafted onto the phenolic hydroxyl group of the lignin through a chemical catalysis method, and then esterified with acrylic acid to prepare epoxy.
  • Lignin acrylate solution to improve lignin's stickiness and castability at high temperatures.
  • Hot pressing molding press the wet lignin-cellulose composite paper at room temperature with a load of 5kg for 10 minutes, and then hot-press at 100°C and 5MPa for 90 minutes to obtain a modified LIG substrate.
  • the modified LIG substrate can be stored at 50% relative humidity (RH) and 23°C.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the laser can also be in the form of a pulse, with a pulse duration of 14 ⁇ s, a maximum power of 40 W, a grating transverse speed of 23 in/s, a focal length of 35 mm, and a laser beam size of about 100 ⁇ m.
  • the laser scanning rate can be 30% of its full speed, and the laser intensity can be 50%, 60%, 70% and 80% of the full power.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of the modified laser-induced graphene material.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • Lignin-based epoxy acrylate is made of lignin as raw material, synthesized by epoxy resin and acrylic acid, and then formed good cross-linking with cellulose in the DMSO system. After hot pressing, a high-strength, flexible, and waterproof composite is obtained. Paper.
  • One embodiment of the present invention provides a method for preparing a modified laser-induced graphene substrate.
  • the laser graphene precursor is lignin.
  • the specific steps include:
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • Modification of lignin includes oxidation, reduction, hydrolysis, alcoholysis, acidolysis of methoxy groups, carboxyl groups, photolysis, esterification, sulfonation, alkylation, halogenation, nitration, Various chemical reactions such as polycondensation, grafting, esterification, and copolymerization enhance the resistance and char-forming properties of lignin. Modification mainly occurs on the phenolic hydroxyl groups in lignin.
  • the lignin is grafted and esterified, and the epoxy group is grafted onto the phenolic hydroxyl group of the lignin through a chemical catalysis method, and then esterified with acrylic acid to prepare epoxy.
  • Lignin acrylate solution to improve lignin's stickiness and castability at high temperatures.
  • a flame retardant group is grafted onto the lignin.
  • the flame retardant group includes a halogen group, a phosphorus group, and a silicon group.
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-110°C and the preferred pressure is 5 -10MPa.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • LIG substrate surface withstands The laser intensity needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the quality of the laser-induced graphene prepared by it can be improved, such as improving the conductivity and hydrophobicity of the laser-induced graphene.
  • the strength and flexibility of the LIG substrate can also be improved.
  • One embodiment of the present invention provides a method for preparing doped graphene materials. Specific steps include:
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, the preferred added amount of lignin is 29wt%, and the preferred cellulose diameter is >1000nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C and the preferred pressure is 5 -10MPa.
  • Doping substances include iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, etc.
  • Iron-based element compounds include ferric chloride, ferric nitrate, nickel chloride, nickel nitrate, cobalt chloride, and cobalt nitrate; manganese compounds include manganese oxide; nitrogen compounds include urea and melamine; boron compounds include boric acid and borate; phosphorus compounds Including phosphoric acid and phosphate; gold compounds include tetrachloroauric acid and potassium cyanoaurate; silver compounds include silver oxide, silver hydroxide, silver sulfide, silver sulfate, silver halide, and silver nitrate.
  • the dopant is sprayed on the LIG substrate in the form of a solution, or the LIG substrate can be immersed in the dopant solution; the solution can be an organic solution, an aqueous solution, etc. containing doping substances, such as ethanol solution, acetone solution, etc. . Volatile substances such as ethanol solution and acetone solution are used as solvents. These volatile solvents evaporate quickly after the doping process, leaving doped substances on the surface of the LIG substrate to facilitate subsequent laser-induced graphene processing. These doping substances can also be attached to the surface of the LIG substrate through deposition.
  • the lignocellulose LIG substrate is irradiated with laser light to convert the precursor in the lignocellulose LIG substrate into graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • the maximum laser power of the laser selected in this embodiment is 10W, and the maximum moving speed of the probe can reach 80mm/s.
  • the power is set to 10% and the probe moving speed is set to 20-50mm/s.
  • One embodiment of the present invention provides a method for preparing doped graphene materials. Specific steps include:
  • the method includes the following steps,
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the lignin addition amount is 0-60wt%, and the preferred lignin addition amount is 10-40wt%.
  • Preferred cellulose diameter is >1500 nm.
  • the doping substances include iron element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, and silver elements. wait.
  • Iron-based element compounds include ferric chloride, ferric nitrate, nickel chloride, nickel nitrate, cobalt chloride, and cobalt nitrate;
  • manganese compounds include manganese oxide; nitrogen compounds include urea and melamine;
  • boron compounds include boric acid and borate; phosphorus compounds Including phosphoric acid and phosphate; gold compounds include tetrachloroauric acid and potassium cyanoaurate; silver compounds include silver oxide, silver hydroxide, silver sulfide, silver sulfate, silver halide, and silver nitrate.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C and the preferred pressure is 5 -10MPa.
  • the lignocellulose LIG substrate is irradiated with laser light to convert the precursor in the lignocellulose LIG substrate into graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO 2 lasers, red lasers, blue lasers Optical devices, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • the maximum laser power of the laser selected in this embodiment is 20W, and the maximum moving speed of the probe can reach 80mm/s.
  • the power is set to 10-30% and the probe moving speed is set to 10-30mm/s.
  • Doping can further improve the performance of LIG products, such as LIG surface resistance, IG / ID parameters, etc.
  • One embodiment of the present invention provides a method for preparing doped graphene materials.
  • the method uses a laser-induced method to convert a LIG substrate into laser-induced graphene.
  • the LIG substrate can be doped with iron-based elements.
  • Specific implementation methods include:
  • LIG substrate contains cellulose.
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters. After irradiation, laser-induced graphene composite materials were obtained.
  • Optional doping substances include iron-based element compounds, manganese compounds, nitrogen compounds, boron compounds, boron elements, phosphorus compounds, gold compounds, silver compounds, gold elements, silver elements, etc.
  • Iron-based element compounds include ferric chloride, ferric nitrate, nickel chloride, nickel nitrate, cobalt chloride, and cobalt nitrate;
  • manganese compounds include manganese oxide; nitrogen compounds include urea and melamine;
  • boron compounds include boric acid and borate; phosphorus compounds Including phosphoric acid and phosphate; gold compounds include tetrachloroauric acid and potassium cyanoaurate; silver compounds include silver oxide, silver hydroxide, silver sulfide, silver sulfate, silver halide, and silver nitrate.
  • the doping method is to attach these doping substances to the surface of laser-induced graphene composite materials through spraying, dipping, deposition and other methods.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the laser-induced graphene composite can be irradiated single or multiple times using the laser with the above parameters. After irradiation, a doped laser-induced graphene composite material is obtained.
  • One embodiment of the present invention provides a method for preparing doped graphene materials.
  • the method uses a laser-induced method to convert a LIG substrate into laser-induced graphene.
  • the LIG substrate can be doped with iron-based elements.
  • Specific implementation methods include:
  • LIG substrate contains cellulose.
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the LIG substrate can also be hot-pressed kraft paper.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters. After irradiation, laser-induced graphene composite materials were obtained.
  • the dopant is attached to the laser-induced graphene composite material by dropping, spraying, and dipping.
  • the molar ratio of the doping material FeCl 3 :NiCl 2 in the dopant is (0.5-1.5): (0.5-1.5), and the solvent in the dopant is ethanol or acetone.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the laser-induced graphene composite can be irradiated single or multiple times using the laser with the above parameters. After irradiation, a doped laser-induced graphene composite material is obtained.
  • the preferred laser power is 5% of full power 80W and the scan rate is 60mm/s.
  • the doped laser-induced graphene composite material prepared by this process has a multi-layered structure in the form of a "sandwich", that is, the doped laser-induced graphene composite material in the "sandwich” form includes a base material layer, a graphene functional layer, Doped layer, graphene functional layer.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • LIG base material layer containing cellulose and lignin.
  • the lignin content of the LIG base material layer is 21wt%, the lignin particle size is >500nm, and the cellulose diameter is 15-30um.
  • Laser scanning of the LIG substrate layer induces the surface of the LIG substrate layer to form a graphene functional layer.
  • the laser used is a CO2 laser, the laser intensity is 20-32W, the laser movement speed is 175mm/s, and the laser focal length is 0.
  • the specific parameters and parameters of laser-induced graphene are as follows.
  • One embodiment of the present invention provides a method for preparing a graphene composite material, which uses a laser to convert a substrate containing cellulose into graphene. Specific steps include:
  • LIG base material containing cellulose and lignin.
  • the lignin content of the LIG base material is 21wt%, the lignin particle size is >500nm, and the cellulose diameter is 15-30um.
  • Laser scanning of the LIG substrate induces the surface of the LIG substrate to transform into a graphene functional layer.
  • the laser used is a CO2 laser, the laser intensity is 32W, the laser movement speed is 175mm/s, and the laser focal length is 0.5-2.5mm.
  • the specific parameters and parameters of laser-induced graphene are as follows.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • Lignin modification Modification of lignin includes oxidation, reduction, hydrolysis, alcoholysis, acidolysis of methoxyl group, carboxyl group, photolysis, phthalation, sulfonation, alkylation, halogenation, nitration, Various chemical reactions such as polycondensation, grafting, esterification, and copolymerization enhance the resistance and char-forming properties of lignin.
  • the lignin is grafted and esterified, and the epoxy group is grafted onto the phenolic hydroxyl group of the lignin through a chemical catalysis method, and then esterified with acrylic acid to prepare epoxy.
  • Lignin acrylate solution to improve lignin's stickiness and castability at high temperatures.
  • LIG substrate preparation and flame retardant treatment the method includes the following steps,
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C and the preferred pressure is 5 -10MPa.
  • Flame retardant treatment spray flame retardant on the surface of the lignocellulose LIG substrate, or use flame retardant to infiltrate the lignocellulose LIG substrate.
  • Flame retardants can be organic flame retardants or inorganic flame retardants.
  • Inorganic flame retardants can be ferric chloride solution, ferric nitrate solution, phosphoric acid, boric acid, etc.; they can also be halogen flame retardants and non-halogen flame retardants.
  • Halogen flame retardants can be organic chlorides and organic bromides.
  • the LIG base material After flame-retardant treatment of the LIG base material, the LIG base material has flame retardant effect and high temperature resistance, improves the ignition point of the LIG base material, and imitates the LIG base material to burn under the laser.
  • the LIG substrate does not require protective gas during the laser scanning process, reducing costs and equipment complexity.
  • the laser power can be increased, the scanning rate can be increased, and the production efficiency can be increased.
  • the surface resistance of biomass LIG dropped from 2000 ⁇ /square to 80 ⁇ /square.
  • Laser-induced scanning uses laser to irradiate the lignocellulose LIG substrate to convert the precursor in the lignocellulose LIG substrate into laser-induced graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the power range of the laser is 30W, and the irradiation power can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate containing the cellulose component can be utilized.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • the method includes the following steps,
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 40-90°C and the preferred pressure is 5 -12MPa.
  • Laser-induced scanning uses laser to irradiate the lignocellulose LIG substrate to convert the precursor in the lignocellulose LIG substrate into laser-induced graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • the protective gas can be reducing and inert gases, such as H 2 , Ar, N 2 , SF 6 or a mixture of several gases.
  • reducing or inert gas as protective gas can effectively enhance the hydrophobicity of the surface of the graphene functional layer, and can replace the flame retardant treatment step of the biomass LIG substrate; scanning in an SF 6 atmosphere can deposit fluorine elements on the graphite In the graphene functional layer, the graphene functional layer is modified.
  • One embodiment of the present invention provides a roll-to-roll production method of layered graphene composite materials, which method includes:
  • the cellulose layered material is soaked into the lignin solution through the first roller unit to obtain a lignin and cellulose LIG base material.
  • the lignin and cellulose LIG substrate is hot-pressed and formed through the second roller unit.
  • the first laser is used to perform laser-induced scanning on the hot-pressed lignin and cellulose LIG substrate to generate a graphene functional layer on the surface of the LIG substrate.
  • the composite material with graphene on the surface is immersed in the modification/catalysis/doping solution through the third roller unit.
  • the modified graphene composite material is laser scanned again with the second laser to obtain the modified graphene composite material.
  • the inventor provides a roll-to-roll transfer device for layered graphene composite materials, which includes: a first roller unit that forms a LIG substrate; and a second roller unit that passes the LIG substrate to be provided by the first roller unit Perform hot pressing molding; and the first laser, which converts the LIG substrate surface provided by the second roller unit into laser-induced graphene to form a graphene layered composite material; and the third roller unit, which will modify/catalyze/ The doping solution is infiltrated into the graphene layered composite material; and the second laser irradiates the graphene layered composite material soaked with the modification/catalysis/doping solution.
  • the roll-to-roll processing graphene layered material production method provided by this embodiment, the process is shown in Figure 8, solves the problem of low laser-induced graphene production efficiency caused by single discontinuous laser irradiation.
  • the problem is to realize the large-scale preparation of graphene composite materials on biomass-containing LIG substrates.
  • the roll-to-roll graphene layered material production method has the advantages of fast production speed, cheap equipment, low substrate cost, and high output.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • Lignin modification Modification of lignin includes oxidation, reduction, hydrolysis, alcoholysis, acidolysis of methoxyl group, carboxyl group, photolysis, phthalation, sulfonation, alkylation, halogenation, nitration, Various chemical reactions such as polycondensation, grafting, esterification, and copolymerization enhance the resistance and char-forming properties of lignin.
  • the lignin is grafted and esterified, and the epoxy group is grafted onto the phenolic hydroxyl group of the lignin through a chemical catalysis method, and then esterified with acrylic acid to prepare epoxy.
  • Lignin acrylate solution to improve lignin's stickiness and castability at high temperatures.
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • Preferred cellulose diameters are >1000 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C and the preferred pressure is 5 -10MPa.
  • Catalyst modification add a catalyst to the surface of the lignocellulose LIG substrate.
  • the catalyst is an ethanol solution of metal, metal alloy, metal/metal oxide mixture, etc.
  • the lignocellulose LIG substrate is irradiated with laser light to convert the precursor in the lignocellulose LIG substrate into graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • the maximum laser power of the laser selected in this embodiment is 10W, and the maximum moving speed of the probe can reach 80mm/s.
  • the power is set to 10% and the probe moving speed is set to 20-50mm/s.
  • One embodiment of the present invention provides a method for preparing graphene composite materials. Specific steps include:
  • the method includes the following steps,
  • Organic solvent extraction and classification using organic solvents such as acetone, butanol, ethanol, etc. to extract and classify lignin, control the molecular weight and particle size of lignin, remove non-functional components, and increase the relative content of active groups. Enhance the processability of lignin.
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add cellulose or nanocellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the lignin addition amount is 0-60wt%, and the preferred lignin addition amount is 10-40wt%.
  • Preferred cellulose diameter is >1500 nm.
  • the lignocellulose wet film is solidified into a film at 40-150°C and 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C and the preferred pressure is 5 -10MPa.
  • the lignocellulose LIG substrate is irradiated with laser light to convert the precursor in the lignocellulose LIG substrate into graphene.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 450-480nm, or 1053nm.
  • Lasers include CO2 lasers, red lasers, blue lasers, femtosecond lasers, etc.
  • the laser power range is 0-50W.
  • the laser intensity endured by the surface of the LIG substrate needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • Single or multiple irradiations of the same area of the LIG substrate can be utilized.
  • the LIG substrate contains cellulose components.
  • the maximum laser power of the laser selected in this embodiment is 20W, and the maximum moving speed of the probe can reach 80mm/s.
  • the power is set to 10-30% and the probe moving speed is set to 10-30mm/s.
  • Doping can further improve the performance of LIG products, such as LIG surface resistance, IG/ID parameters, etc.
  • This embodiment provides a graphene supercapacitor, which includes a packaging container, a core packaged in the packaging container, and a current collector partially inserted into the packaging container and connected to the graphene functional layer in the core.
  • the core is a roll-shaped structure wound by a separator, electrolyte and graphene composite material.
  • the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the electrolyte.
  • the structure of the separator and the electrolyte may be a stacked liquid-absorbent separator, and the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the liquid-absorbent separator.
  • the liquid-absorbing diaphragm absorbs electrolyte.
  • the graphene composite material in the graphene supercapacitor described in this embodiment includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is transferred It becomes carbonized cellulose; molecules of part of cellulose and carbonized cellulose are entangled with each other to form a network structure, and laser-induced graphene is nested in this network structure.
  • the nested structure is shown in Figure 17.
  • the core of the graphene supercapacitor described in this embodiment is rolled into a roll shape by two layers of the graphene composite material and the liquid-absorbent separator laminated between the two layers of the graphene composite material.
  • the current collector includes a positive current collector connected to the graphene functional layer of one of the flexible graphene composite materials and a negative current collector connected to the graphene functional layer of another of the graphene composite materials.
  • the current collector is bonded to the graphene functional layer through conductive glue.
  • the packaging container includes a cylinder with one end closed and the other end open, and a sealing plug for blocking the open end of the cylinder, wherein the current collector sealingly penetrates the sealing plug.
  • the structural schematic diagram of the supercapacitor is shown in Figure 18, Figure 22, and Figure 23.
  • the supercapacitor exhibits good energy-power performance.
  • Some performance parameters are as follows. Taking LBEA-A-1-2 as an example, this number represents lignin-based epoxy acrylate (LBEA) with different content.
  • the LEBA is a precursor material for making graphene composite materials, where A represents the organic material used.
  • Solvent-soluble lignin is acetone-soluble lignin (B represents butanol-soluble lignin, and E represents ethanol-soluble lignin).
  • 1 represents organic solvent-soluble lignin dissolved in 100 mL of ethanol in an amount of 1 g.
  • DMSO methyl sulfoxide
  • 2 represents the addition of 2 grams of epichlorohydrin (ECH) per 1g of lignin:
  • This embodiment provides a graphene supercapacitor and a method for preparing the graphene composite material used therein.
  • the graphene supercapacitor includes a packaging container and a core packaged in the packaging container, and is partially inserted into the packaging container and connected to the core.
  • the inner graphene functional layer is connected to the current collector.
  • the core is a roll-shaped structure wound by a separator, electrolyte and graphene composite material.
  • the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the electrolyte.
  • the structure of the separator and the electrolyte may be a stacked liquid-absorbent separator, and the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the liquid-absorbent separator.
  • the liquid-absorbing diaphragm absorbs electrolyte.
  • the graphene composite material in the graphene supercapacitor described in this embodiment includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the core of the graphene supercapacitor described in this embodiment is rolled into a roll shape by two layers of the graphene composite material and the liquid-absorbent separator laminated between the two layers of the graphene composite material.
  • the current collector includes a positive current collector connected to the graphene functional layer of one of the flexible graphene composite materials and a negative current collector connected to the graphene functional layer of another of the graphene composite materials.
  • the current collector is bonded to the graphene functional layer through conductive glue.
  • the packaging container includes a cylinder with one end closed and the other end open, and a sealing plug for blocking the open end of the cylinder, wherein the current collector sealingly penetrates the sealing plug.
  • the structural schematic diagram of the supercapacitor is shown in Figure 18, Figure 22, and Figure 23.
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better attached to the base material surface. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • This embodiment provides a graphene supercapacitor, which includes a packaging container, a core packaged in the packaging container, and a current collector partially inserted into the packaging container and connected to the graphene functional layer in the core.
  • the core is a roll-shaped structure wound by a separator, electrolyte and graphene composite material.
  • the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the electrolyte.
  • the structure of the separator and the electrolyte may be a stacked liquid-absorbent separator, and the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the liquid-absorbent separator.
  • the liquid-absorbing diaphragm absorbs electrolyte.
  • the graphene composite material in the graphene supercapacitor described in this embodiment includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the number of graphene composite materials in the graphene supercapacitor described in this embodiment is one.
  • the graphene functional layer includes a graphene positive electrode functional layer and a graphene negative electrode functional layer.
  • the graphene positive electrode functional layer and The graphene negative electrode functional layer is provided on the substrate layer and does not contact each other.
  • the current collector includes a positive current collector and a negative current collector connected to the graphene positive electrode functional layer and the graphene negative electrode functional layer respectively.
  • the current collector is bonded to the graphene functional layer through conductive glue.
  • the packaging container includes a cylinder with one end closed and the other end open, and a sealing plug for blocking the open end of the cylinder, wherein the current collector sealingly penetrates the sealing plug.
  • the structural schematic diagram of the supercapacitor is shown in Figure 18, Figure 22, and Figure 24.
  • This embodiment provides a graphene supercapacitor and a method for preparing the graphene composite material used therein.
  • the graphene supercapacitor includes a packaging container and a core packaged in the packaging container, and is partially inserted into the packaging container and connected to the core.
  • the inner graphene functional layer is connected to the current collector.
  • the core is a roll-shaped structure wound by a separator, electrolyte and graphene composite material.
  • the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the electrolyte.
  • the structure of the separator and the electrolyte may be a stacked liquid-absorbent separator, and the graphene functional layer in the graphene supercapacitor is disposed on the surface of the base material layer adjacent to the liquid-absorbent separator.
  • the liquid-absorbing diaphragm absorbs electrolyte.
  • the graphene composite material in the graphene supercapacitor described in this embodiment includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is transferred It becomes carbonized cellulose; molecules of part of cellulose and carbonized cellulose are entangled with each other to form a network structure, and laser-induced graphene is nested in this network structure.
  • the nested structure is shown in Figure 17.
  • the number of graphene composite materials in the graphene supercapacitor described in this embodiment is one.
  • the graphene functional layer includes a graphene positive electrode functional layer and a graphene negative electrode functional layer.
  • the graphene positive electrode functional layer and The graphene negative electrode functional layer is provided on the substrate layer and does not contact each other.
  • the current collector includes a positive current collector and a negative current collector connected to the graphene positive electrode functional layer and the graphene negative electrode functional layer respectively.
  • the current collector is bonded to the graphene functional layer through conductive glue.
  • the packaging container includes a cylinder with one end closed and the other end open, and a sealing plug for blocking the open end of the cylinder, wherein the current collector sealingly penetrates the sealing plug.
  • the structural schematic diagram of the supercapacitor is shown in Figure 18, Figure 22, and Figure 24.
  • One embodiment of the present invention provides a roll-to-roll production method of the above-mentioned graphene composite material, which can continuously prepare the above-mentioned graphene composite material, thereby realizing large-scale production of supercapacitors.
  • Specific implementation methods include:
  • the cellulose layered material is soaked into the lignin solution through the first roller unit to obtain a lignin and cellulose LIG base material.
  • the lignin and cellulose LIG substrate is hot-pressed and formed through the second roller unit.
  • the first laser is used to perform laser-induced scanning on the hot-pressed lignin and cellulose LIG substrate to generate a graphene functional layer on the surface of the LIG substrate.
  • the composite material with graphene on the surface can be immersed in the modification/catalysis/doping solution through a third roller unit.
  • the modified graphene composite material is laser scanned again with the second laser to obtain the modified graphene composite material.
  • the inventor provides a roll-to-roll transfer device for layered graphene composite materials, which includes: a first roller unit that forms a LIG substrate; and a second roller unit that passes the LIG substrate to be provided by the first roller unit Perform hot pressing molding; and the first laser, which converts the LIG substrate surface provided by the second roller unit into laser-induced graphene to form a graphene layered composite material; and the third roller unit, which will modify/catalyze/ The doping solution is infiltrated into the graphene layered composite material; and the second laser irradiates the graphene layered composite material soaked with the modification/catalysis/doping solution.
  • the roll-to-roll processing graphene layered material production method provided by this embodiment, the process is shown in Figure 8, solves the problem of low laser-induced graphene production efficiency caused by single discontinuous laser irradiation.
  • the problem is to realize the large-scale preparation of graphene composite materials on biomass-containing LIG substrates.
  • the roll-to-roll graphene layered material production method has the advantages of fast production speed, cheap equipment, low substrate cost, and high output.
  • This embodiment provides a graphene supercapacitor, which includes a capacitor body that includes a plurality of single capacitors and inner tabs.
  • the monomer capacitors include a graphene positive electrode composed of graphene core material, a graphene negative electrode and an electrolyte, and the The graphene positive electrode of the single capacitor and the graphene negative electrode of the first adjacent single capacitor are integrally connected through the inner tab, and the graphene negative electrode of the single capacitor and the graphene positive electrode of the second adjacent single capacitor are connected through the inner electrode.
  • the graphene positive electrode and the graphene negative electrode are in any one of interdigitated shapes, parallel strip shapes, spiral shapes or a combination thereof.
  • the outer packaging is used to package the capacitor body. Schematic diagrams of the supercapacitor in this embodiment are shown in Figures 25 and 26.
  • the functions of the tabs and the current collector are mainly to collect the current generated inside the device so as to form a larger current for external output.
  • the graphene composite material in the graphene supercapacitor described in this embodiment includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the laser can be a CO 2 laser light source.
  • the LIG precursor can be PI, GO film, PI-LSG+Ni-CATMOF, PI-LSG+PANI, PI-LSG+MnO 2 , PI-LSG+FeOOH/LSG+MnO 2 , PI-LSG+Fe 3 O 4 /LSG, Hydrated GO film, H 3 BO 3 /PI.
  • the electrolyte can be one of Hydrated GO, H 2 SO 4 , BMIM-BF 4 , PVA/H 2 SO 4 , BMIM, and PVA/LiCl.
  • the voltage range of the corresponding supercapacitor is 0.3-250V, and the CA is 0 -1000mF ⁇ cm -2 , Cv is 0-150F ⁇ cm -3 , Ev is 0-110mWh ⁇ cm -3 , Pv is 0-100W ⁇ cm -3 .
  • the LIG precursor can be GO/HAuCl 4 , GO/Ni, GO film, PI, GO film, PI-LSG+Ni-CATMOF, PI-LSG+PANI, PI- One of LSG+MnO 2 , PI-LSG+FeOOH/LSG+MnO 2 , PI-LSG+Fe 3 O 4 /LSG, Hydrated GO film, and H 3 BO 3 /PI.
  • the electrolyte can be one of FS-IL, Hydrated GO, H2SO4, BMIM-BF4, PVA/H2SO4, BMIM, PVA/LiCl.
  • the corresponding supercapacitor voltage range is 0.3-250V and CA is 0-1000mF ⁇ cm -2 , Cv is 0-150F ⁇ cm -3 , Ev is 0-110mWh ⁇ cm -3 , Pv is 0-2500W ⁇ cm -3 .
  • This embodiment provides a graphene supercapacitor, which includes a capacitor body that includes a plurality of single capacitors and inner tabs.
  • the monomer capacitors include a graphene positive electrode composed of graphene core material, a graphene negative electrode and an electrolyte, and the The graphene positive electrode of the single capacitor and the graphene negative electrode of the first adjacent single capacitor are integrally connected through the inner tab, and the graphene negative electrode of the single capacitor and the graphene positive electrode of the second adjacent single capacitor are connected through the inner electrode.
  • the ears are integrally connected; the graphene positive electrode and the graphene negative electrode are in any one of interdigitated shapes, parallel strip shapes, spiral shapes or a combination thereof.
  • the outer packaging is used to package the capacitor body. Schematic diagrams of the supercapacitor in this embodiment are shown in Figures 25 and 26.
  • the graphene composite material in the graphene supercapacitor described in this embodiment includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • This embodiment provides a graphene strain sensor, which is used to improve the application range and application scenarios of the graphene strain sensor.
  • the graphene strain sensor includes a conductive layer composed of graphene composite material. The relevant schematic diagrams of the strain sensor are shown in Figure 19, Figure 27, and Figure 28.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the conductive layer includes a stacked structure formed by a base material layer and a graphene functional layer.
  • the conductive layer in the graphene strain sensor may include a stack structure formed by a base material layer and a multi-layer graphene functional layer stack.
  • it may be composed of a base material layer and a double-layer graphene functional layer stack, or it may be composed of a base material layer and a double-layer graphene functional layer stack. It consists of three stacks of graphene functional layers.
  • the multi-layer graphene functional layers in the conductive layer are stacked, but the force between the graphene functional layers is weaker than the force between the single-layer graphene functional layers themselves.
  • the graphene strain sensor further includes a connecting electrode, which includes a first electrode and a second electrode; the first electrode and the second electrode are respectively provided at opposite ends of the conductive layer.
  • Some performance parameters of the strain sensor are: when bending downward (stretching), when the bending degree increases from 0 to 10mm under ambient conditions (sensitivity is 3.29 ⁇ /mm), the sensor resistance (LIG on the convex side ) increases from 43 to 76 ⁇ ; when bent upward (compressed), the resistance (LIG on the concave side) drops from 43 ⁇ to 19 ⁇ (sensitivity is 2.55 ⁇ /mm).
  • the performance of the wearable sensor is affected by the epoxy acrylate content in LBEA.
  • the tensile sensitivities of the LBEA-A-10-1 and LBEA-A-10-0.5 derived LIG sensors are 3.10 and 1.96 ⁇ /mm, respectively, the compression sensitivities are 2.20 and 2.02 ⁇ /mm, respectively, and the measurement ranges are ⁇ 8 and ⁇ 5mm.
  • This embodiment provides a graphene strain sensor, which is used to improve the application range and application scenarios of the graphene strain sensor.
  • the graphene strain sensor includes a conductive layer composed of graphene composite material. The relevant schematic diagrams of the strain sensor are shown in Figure 19, Figure 27, and Figure 28.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the conductive layer includes a stacked structure formed by a base material layer and a graphene functional layer.
  • the conductive layer in the graphene strain sensor may include a stack structure formed by a base material layer and a multi-layer graphene functional layer stack.
  • it may be composed of a base material layer and a double-layer graphene functional layer stack, or it may be composed of a base material layer and a double-layer graphene functional layer stack. It consists of three stacks of graphene functional layers.
  • the multi-layer graphene functional layers in the conductive layer are stacked, but the force between the graphene functional layers is weaker than the force between the single-layer graphene functional layers themselves.
  • the graphene strain sensor further includes a connecting electrode, which includes a first electrode and a second electrode; the first electrode and the second electrode are respectively provided at opposite ends of the conductive layer.
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • Some performance parameters of the strain sensor are: when bending downward (stretching), when the bending degree increases from 0 to 10mm under ambient conditions (sensitivity is 3.29 ⁇ /mm), the sensor resistance (LIG on the convex side ) increases from 43 to 76 ⁇ ; when bent upward (compressed), the resistance (LIG on the concave side) drops from 43 ⁇ to 19 ⁇ (sensitivity is 2.55 ⁇ /mm).
  • the performance of the wearable sensor is affected by the epoxy acrylate content in LBEA.
  • the tensile sensitivities of the LBEA-A-10-1 and LBEA-A-10-0.5 derived LIG sensors are 3.10 and 1.96 ⁇ /mm, respectively, the compression sensitivities are 2.20 and 2.02 ⁇ /mm, respectively, and the measurement ranges are ⁇ 8 and ⁇ 5mm.
  • This embodiment provides a graphene strain sensor, which includes: a graphene composite material containing a base material layer and a graphene functional layer; electrodes connected to the base material layer and the graphene functional layer respectively; A plasticized layer is formed between the electrode and the base material layer. Further, the graphene composite material is a flexible graphene composite material. The relevant schematic diagrams of the strain sensor are shown in Figure 19, Figure 27, and Figure 28.
  • the flexible graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the plasticized layer of the graphene strain sensor is a flexible tape with an adhesive or a film without an adhesive.
  • the plasticized layer can reduce the deformation of the area covered by the plasticized layer when the device is strained, and protect the electrodes thereon so that their resistance does not change.
  • the electrode is a conductive material, and the electrode is used to connect the graphene functional layer and connect the lead wire.
  • the boundary between the electrode and the graphene functional layer is covered with a stress buffer layer, which is used to release the stress at the boundary between the electrode and the graphene functional layer and enhance the electrical connection between the electrode and the graphene functional layer when the device is strained. .
  • Some performance parameters of the strain sensor are: when bending downward (stretching), when the bending degree increases from 0 to 10mm under ambient conditions (sensitivity is 3.29 ⁇ /mm), the sensor resistance (LIG on the convex side ) increases from 43 to 76 ⁇ ; when bent upward (compressed), the resistance (LIG on the concave side) drops from 43 ⁇ to 19 ⁇ (sensitivity is 2.55 ⁇ /mm).
  • the performance of the wearable sensor is affected by the epoxy acrylate content in LBEA.
  • the tensile sensitivities of the LBEA-A-10-1 and LBEA-A-10-0.5 derived LIG sensors are 3.10 and 1.96 ⁇ /mm, respectively, the compression sensitivities are 2.20 and 2.02 ⁇ /mm, respectively, and the measurement ranges are ⁇ 8 and ⁇ 5mm.
  • This embodiment provides a graphene strain sensor, which includes: a graphene composite material containing a base material layer and a graphene functional layer; electrodes connected to the base material layer and the graphene functional layer respectively; A plasticized layer is formed between the electrode and the base material layer. Further, the graphene composite material is a flexible graphene composite material. The relevant schematic diagrams of the strain sensor are shown in Figure 19, Figure 27, and Figure 28.
  • the flexible graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the plasticized layer of the graphene strain sensor is a flexible tape with an adhesive or a film without an adhesive.
  • the plasticized layer can reduce the deformation of the area covered by the plasticized layer when the device is strained, and protect the electrodes thereon so that their resistance does not change.
  • the electrode is a conductive material, and the electrode is used to connect the graphene functional layer and connect the lead wire.
  • the boundary between the electrode and the graphene functional layer is covered with a stress buffer layer, which is used to release the stress at the boundary between the electrode and the graphene functional layer and enhance the electrical connection between the electrode and the graphene functional layer when the device is strained. .
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and Picosecond laser laser, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and cannot effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • Some performance parameters of the strain sensor are: when bending downward (stretching), when the bending degree increases from 0 to 10mm under ambient conditions (sensitivity is 3.29 ⁇ /mm), the sensor resistance (LIG on the convex side ) increases from 43 to 76 ⁇ ; when bent upward (compressed), the resistance (LIG on the concave side) drops from 43 ⁇ to 19 ⁇ (sensitivity is 2.55 ⁇ /mm).
  • the performance of the wearable sensor is affected by the epoxy acrylate content in LBEA.
  • the tensile sensitivities of the LIG sensors derived from LBEA-A-10-1 and LBEA-A-10-0.5 are 3.10 and 1.96 ⁇ /mm respectively, the compression sensitivities are 2.20 and 2.02 ⁇ /mm respectively, and the measurement ranges are ⁇ 8 and ⁇ 5mm.
  • This embodiment provides a graphene Joule heater, which includes a graphene composite material. Electrodes are pasted on both ends of the graphene composite material. The joints between the electrodes and the graphene composite material are coated with conductive silver. paint.
  • the graphene Joule heater can heat the heating area covered by the graphene composite material.
  • the heating method includes attaching the graphene Joule heater to the surface of the object or embedding it inside the object for heating; specifically, using a power supply
  • the positive and negative electrodes are respectively connected to the two electrodes of the graphene Joule heater, and electrical power is input.
  • the laser-induced graphene paper heater converts the electrical energy into Joule heat to heat the object.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the Joule heater has excellent heating performance, and some of its performance parameters are: the maximum heating rate is approximately 3.21°C/s.
  • the steady-state temperature of the LIG increases from 28.7 to 125°C accordingly.
  • the voltage intensity increases from 1 to 5V/cm 2
  • the equilibrium temperatures of the LIG heaters derived from LBEA-A-10-2, LBEA-E-10-2, and LBEA-B-10-2 increase from 29.7 to 28.7, respectively. and 29.0°C to 131.2, 125.1 and 91.3°C.
  • This embodiment provides a graphene Joule heater, which includes a graphene composite material. Electrodes are pasted on both ends of the graphene composite material. The joints between the electrodes and the graphene composite material are coated with conductive silver. paint.
  • the graphene Joule heater can heat the heating area covered by the graphene composite material.
  • the heating method includes attaching the graphene Joule heater to the surface of the object or embedding it inside the object for heating; specifically, using a power supply
  • the positive and negative electrodes are respectively connected to the two electrodes of the graphene Joule heater, and electrical power is input.
  • the laser-induced graphene paper heater converts the electrical energy into Joule heat to heat the object.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • the Joule heater has excellent heating performance, and some of its performance parameters are: the maximum heating rate is approximately 3.21°C/s.
  • the steady-state temperature of the LIG increases from 28.7 to 125°C accordingly.
  • the voltage intensity increases from 1 to 5V/cm 2
  • the equilibrium temperatures of the LIG heaters derived from LBEA-A-10-2, LBEA-E-10-2, and LBEA-B-10-2 increase from 29.7 to 28.7, respectively. and 29.0°C to 131.2, 125.1 and 91.3°C.
  • This embodiment provides a dopamine sensor based on graphene composite material.
  • the dopamine sensor includes electrodes attached to both ends of the graphene composite material, and the joint between the electrode and the graphene composite material is coated with conductive silver paint.
  • the surface of the electrode is modified with a graphene composite material, and then the ractopamine antigen is dropped on the modified electrode to obtain an electrochemical immunosensor for detecting ractopamine.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • This embodiment provides a dopamine sensor based on graphene composite material.
  • the dopamine sensor includes electrodes attached to both ends of the graphene composite material, and the joint between the electrode and the graphene composite material is coated with conductive silver paint.
  • the surface of the electrode is modified with a graphene composite material, and then the ractopamine antigen is dropped on the modified electrode to obtain an electrochemical immunosensor for detecting ractopamine.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • the graphene gas sensor includes a graphene composite material.
  • the graphene composite material includes a base material layer and a graphene functional layer.
  • the graphene functional layer is used as a graphene electrode; the graphene gas sensor is sensitive to the location where it is located. Detect the gas to be measured in the environment and output an electrical signal used to characterize the concentration of the gas to be measured, including: when the graphene gas sensor is placed in a gas environment, the surface of the graphene electrode material adsorbs gas molecules to cause resistivity changes, and then outputs an electrical signal used to characterize the gas concentration.
  • the microprocessor converts the electrical signal value corresponding to the output electrical signal used to represent the gas concentration to be measured into the gas concentration value to be measured.
  • the relevant schematic diagrams of the gas sensor in the embodiment are shown in Figures 29 and 30.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • the graphene electrode has the highest sensitivity to H 2 , followed by CO 2 , compressed air and N 2 . Average response and recovery times are approximately 12 and 18 seconds respectively.
  • the graphene gas sensor includes a graphene composite material.
  • the graphene composite material includes a base material layer and a graphene functional layer.
  • the graphene functional layer is used as a graphene electrode; the graphene gas sensor is sensitive to the location where it is located. Detect the gas to be measured in the environment and output an electrical signal used to characterize the concentration of the gas to be measured, including: when the graphene gas sensor is placed in a gas environment, the surface of the graphene electrode material adsorbs gas molecules to cause resistivity changes, and then outputs an electrical signal used to characterize the gas concentration.
  • the microprocessor converts the electrical signal value corresponding to the output electrical signal used to represent the gas concentration to be measured into the gas concentration value to be measured.
  • the relevant schematic diagrams of the gas sensor in the embodiment are shown in Figures 29 and 30.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • One embodiment of the present invention provides a method for preparing the above-mentioned graphene composite material.
  • the method uses laser to irradiate a cellulose-composite precursor-containing LIG substrate to prepare the graphene composite material.
  • Specific implementation methods include:
  • the addition ratio of the precursor can be 2-45wt%, and the preferred addition ratio can be 15-25wt%.
  • the precursor can be graphene oxide, polyimide, or lignin.
  • the wavelength of the laser can be 9.3-10.6 ⁇ m, 625-740nm, 505-566nm, 450-480nm, 10-450nm, 1053nm.
  • Lasers include CO2 lasers, red lasers, green lasers, blue lasers, femtosecond and picosecond lasers, etc.
  • the laser intensity endured by the surface of the LIG substrate needs to be greater than 3J/cm 2 and less than 40J/cm 2 , and the preferred laser intensity is 5.5-20J/cm 2 .
  • the same area of the LIG substrate can be irradiated single or multiple times using the laser with the above parameters.
  • the TEM results of different laser intensities are shown in Figure 14.
  • the laser when the laser is irradiated to the surface of the LIG substrate, it can be focused or scanned out of focus (-3.0-3.0 mm). When scanning out of focus, the laser spot is circular. During the translation process of the laser head, every The group of circles will overlap, and the overlapping area is equivalent to scanning twice or more.
  • the precursor particle size is 10 nm-500 nm, and the cellulose diameter is >1000 nm.
  • the addition of the precursor in an amount greater than 10 wt% is beneficial to wrapping the cellulose fibers, protecting the cellulose from being carbonized during the laser scanning process, and maintaining the stability of the bundle tube structure of the cellulose, so that the final The generated graphene functional layer is better adhered to the surface of the substrate layer. If the amount of precursor added is too low, the precursor covering the cellulose surface will be too thin and unable to effectively protect the cellulose from laser irradiation. Excessive addition of precursor will affect the flexibility of graphene composites.
  • the thickness of the LIG substrate is 0.02-0.5mm.
  • the graphene electrode has the highest sensitivity to H 2 , followed by CO 2 , compressed air and N 2 . Average response and recovery times are approximately 12 and 18 seconds respectively.
  • This embodiment provides an electrode for electro-Fenton water purification and a production method of the electrode.
  • the electrode is based on the graphene composite material provided by the invention, and a direct CO 2 method for directly synthesizing a renewable LIG electrode is proposed.
  • Laser scoring of lignocellulose-based kraft paper includes the following steps:
  • Magnetic FeNi 3 nanoparticles are sandwiched between two LIGs as Fenton catalysts to obtain FeNi 3 LIG electrodes
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • This embodiment provides an electrode for electro-Fenton water purification and a production method of the electrode.
  • the electrode is based on the graphene composite material provided by the invention, and a direct CO 2 method for directly synthesizing a renewable LIG electrode is proposed. Laser scoring of lignocellulose-based kraft paper.
  • the specific steps include the following steps, and the process is shown in Figure 31:
  • the cellulose layered material is soaked into the lignin solution through the first roller unit to obtain a lignin and cellulose LIG base material.
  • the lignin and cellulose LIG substrate is hot-pressed and formed through the second roller unit.
  • the first laser is used to perform laser-induced scanning on the hot-pressed lignin and cellulose LIG substrate to generate a graphene functional layer on the surface of the LIG substrate.
  • the composite material with graphene on the surface is immersed in FeNi3 solution through the third roller unit.
  • the modified graphene composite material was laser scanned again with the second laser to obtain a FeNi 3 LIG electrode.
  • the graphene composite material includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer, as shown in Figures 9 and 10.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and the part that enters the graphene functional layer is converted into carbonized cellulose; the molecules of part of the cellulose and carbonized cellulose are entangled with each other.
  • the knots form a network structure, and the laser-induced graphene is nested in the network structure.
  • the nested structure is shown in Figure 17.
  • This embodiment provides a graphene transfer process. Specific steps include:
  • Silica gel dissolution method for transfer printing Use a glue spreader to evenly pour the silica gel solution on the surface of LIG. After heating and solidification, transfer it to water. The lignin/PVA will dissolve in water and the LIG will be transferred to the flexible and bendable silica gel.
  • This embodiment provides a graphene transfer process. Specific steps include:
  • PVA polyvinyl alcohol
  • LIG Laser direct writing scanning. Adjust the laser parameters and directly scan the laser on the surface of the lignin/PVA film to prepare LIG.
  • the LIG was formed using a 30W, 10.6 ⁇ m CO2 laser cutter (Universal Laser Systems VLS3.50 laser cutter/engraver) under ambient conditions. 1000 pulses per inch (PPI), 10% speed and an additional 2mm Z-axis distance are fixed for all laser processes. Different laser powers of 20%, 30%, and 40% were applied to each precursor in sequence.
  • the laser scanning area is a rectangle with a length of 30mm and a width of 5mm.
  • Silica gel dissolution method for transfer printing Use a glue spreader to evenly pour the silica gel solution on the surface of LIG. After heating and solidification, transfer it to water. The lignin/PVA will dissolve in water and the LIG will be transferred to the flexible and bendable silica gel.
  • One embodiment of the present invention provides a flexible graphene composite material, which includes a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the graphene functional layer contains laser-induced graphene and has a three-dimensional channel structure.
  • part of the cellulose connects the base material layer and the graphene functional layer, and when it enters the graphene functional layer, it is partially transformed into carbonized cellulose; part of the cellulose (containing carbonized cellulose) molecules are entangled with each other.
  • the knots form a network in which some of the laser-induced graphene is nested.
  • the ratio of graphene to laser-induced graphene in the graphene functional layer is 1:1-1:2, and the detection method of the ratio of graphene to laser-induced graphene is TEM detection.
  • I G / ID is 1.0-3.3
  • I 2D /I G is 0.4-0.8
  • L a is 20-45mm.
  • the surface resistance of the graphene functional layer is 18-150 ⁇ /square.
  • the conductivity of the graphene functional layer is 50-200S/cm.
  • the specific surface area of the graphene functional layer is 10-350m 2 /g.
  • the pore diameter of the graphene functional layer is 0-750nm.
  • the thickness of the graphene functional layer is 0.05-35 ⁇ m.
  • the relative content of C of the graphene functional layer is 85wt%-93wt%, the relative content of O is 5wt%-10wt%, and the relative content of N is 2wt%-5wt%, as shown in Figures 3 to 7.
  • the laser light source used is blue light source.
  • the base material layer may be cellulose containing folic acid.
  • Folic acid is used to modify cellulose during preparation, and cellulose forms an intertwined network structure in the base material layer.
  • the air permeability of the folic acid-modified fiber paper base material layer is 1700-2200mL ⁇ mm ⁇ (cm 2 ⁇ h ⁇ mmAq) -1 .
  • the surface resistance range is 90-300 ⁇ /square.
  • One embodiment of the present invention provides a preferred bio-based flexible graphene composite material, including a base material layer and a graphene functional layer, and the graphene functional layer is attached to the surface of the base material layer.
  • the substrate layer includes folic acid-modified cellulose and nano-lignin. Nano-lignin can significantly improve the quality of laser-induced graphene. At the same time, the smaller the particle size of nano-lignin, the better the quality of laser-induced graphene.
  • Nano-lignin can better coat the surface of cellulose and protect the nano-cellulose from being decomposed during laser irradiation. At the same time, nanolignin is converted into laser-induced graphene. Thereby improving the quality of the graphene functional layer.
  • One embodiment of the present invention provides a method for preparing a graphene composite material, which converts a LIG substrate containing cellulose into graphene using a laser. Specific steps include:
  • the lignin purification method includes the following steps:
  • lignin and cellulose mixed solution Preparation of lignin and cellulose mixed solution. Add folic acid and cellulose to the lignin solution, stir, ultrasonic, and emulsify to prepare a lignin-cellulose mixed solution.
  • the added amount of lignin is 0-41wt%, and the preferred added amount of lignin is 29wt%.
  • the preferred cellulose diameter is >1000nm, and the added amount of folic acid is 5-25wt%.
  • the lignocellulose wet film is cured into a film at 40-150°C, 1-15MPa to become the lignocellulose LIG substrate.
  • the preferred temperature is 50-100°C, and the preferred pressure is 5-10MPa.
  • the lignocellulose LIG substrate is irradiated with laser to generate a graphene functional layer on the surface of the lignocellulose LIG substrate.
  • the wavelength of laser is 400-500nm.
  • the laser uses a blue laser.
  • the laser power range is 0-50W.
  • the laser intensity endured by the substrate surface needs to be >3J/cm 2 , and the preferred laser intensity is >5.5J/cm 2 .
  • the power intensity of the laser can be 65%, 70%, 75%, 80%, 85%, 90%, 100%. Single or multiple irradiations of the same area of the substrate can be utilized.

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Abstract

本发明提供了一种激光诱导石墨烯及其制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：制备纤维素复合的包含前驱体的LIG基材，激光照射前驱体。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。本发明的还提供了一种柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中。

Description

一种激光诱导石墨烯及其制备方法 技术领域
本发明涉及石墨烯材料技术领域，尤其涉及一种激光诱导石墨烯层状复合材料及其生产方法。
背景技术
石墨烯即石墨单片层，是碳原子以sp2杂化方式形成具有蜂巢结构的单原子层二维晶体材料。石墨烯是碳纳米材料家族的重要成员，由于其独特的物理性质，如高表面积、高导电性、良好的机械强度和稳定性，其已经在电子器件、能量储存和电化学催化中显示出广阔应用前景。
为了获得高质量的石墨烯，如今已有机械剥离法、化学气相沉积法、表面外延生长法、切割纳米管法、液相剥离法、氧化还原法等。
在实现本发明过程中，发明人发现现有技术中至少存在如下问题：机械剥离法和外延生长法制备效率较低，难以满足大规模的需要。还原氧化石墨烯法应用较多，但其制备过程中使用的还原剂大多具有高毒性、高污染等缺点，为制备过程的保护措施及废液处理增加了成本。化学气相沉积法虽然可以获得大尺寸连续的石墨烯薄膜，但在剥离过程中，可能会引入新的杂质导致石墨烯品质受到影响，同时反应条件苛刻、严格。此外，上述常见生产方法也都是以石墨矿作为原材料，这种矿产资源是不可循环再生的，不利于石墨烯的大规模生产。如何通过低成本、规模化、生产步骤简单、无毒环保的制备方法获得高质量、低成本的石墨烯，成为了这一领域的研究热点。
发明内容
发明人经大量研究发现，传统的石墨烯生产方法存在石墨烯制备成本高、石墨烯制作工艺复杂等诸多不足。激光诱导方法制备石墨烯是一种新型的石墨烯制备方法，其原理为使用激光诱导，使前驱体转化为石墨烯，这种方法可以实现在常温、无保护气氛的条件下，低成本的制备石墨烯材料。
在实现本发明的过程中，发明人发现激光诱导的方法，在制备激光诱导石墨烯(LIG)时容易出现裂纹、不够平整，基材容易发生扭曲、断裂，制备的LIG与基材结合不牢容易脱落等问题。
在实现本发明的过程中，发明人提供了一种石墨烯层状复合材料的制备方法，该方法通过激光将含有纤维素和前驱体的基材层转化激光诱导石墨烯。发明人通过大量研究发现，在进行激光诱导转化的过程中，需要合理的设置激光参数，使得激光深入基材层内部，将前驱体转化为激光诱导石墨烯，同时激光还不破坏基材层中的纤维素，维持基材层的稳定以及基材层与激光诱导石墨烯的连接，从而使得制得的激诱导石 墨烯更好的附着于基材层的表面，解决石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。该制备方法使用的激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。可以使用的激光的波长范围可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。LIG基材表面承受的激光强度需要＞3J/cm2。
在实现本发明的过程中，发明人还提供了一种石墨烯层状复合材料，该石墨烯层状复合材料包括基材层、石墨烯功能层。石墨烯功能层含有激光诱导石墨烯组分。石墨烯层状复合材料中含有纤维素，纤维素分散于基材层与石墨烯功能层。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素分子互相缠结形成网状结构，部分激光诱导石墨烯组分嵌套于该网状结构中。石墨烯层状复合材料因其具备的特殊结构，克服了石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。
在实现本发明的过程中，发明人还提供了一种掺杂激光石墨烯材料，该石墨烯层状复合材料包括基材层、石墨烯功能层。石墨烯功能层含有激光诱导石墨烯。石墨烯功能层还含有杂化物，杂化物包括铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等，以及上述物质的组合。石墨烯层状复合材料中含有纤维素，纤维素分散于基材层与石墨烯功能层。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。石墨烯层状复合材料因其具备的特殊结构，克服了石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。含有杂化物的石墨烯功能层具有优异的性能，如高面电容、高电容量、低面电阻、强选择性等特性。
在实现本发明的过程中，发明人提供了一种掺杂激光石墨烯材料的制备方法，该方法通过激光将含有纤维素和前驱体的基材层转化激光诱导石墨烯。发明人通过大量研究发现，将掺杂物质铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质、硫化合物等引入激光诱导石墨烯基材。发明人还提供了一种掺杂激光石墨烯材料的制备方法，在LIG基材中添加纤维素，并且在进行激光诱导转化的过程中，通过合理的设置激光参数，使得激光深入LIG基材，将前驱体转化为激光诱导石墨烯，将部分纤维素转化为碳化纤维素，同时激光还不破坏碳化纤维素的束管结构和网状结构，维持石墨烯功能层的稳定以及基材层与激光诱导石墨烯的连接，从而使得制得的激诱导石墨烯更好的附着于基材层的表面，解决石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。通过对LIG基材进行掺杂，可以大幅提高激光诱导石墨烯的性能，如提高面电容、提高电容量、降低面电阻、增强选择性等特性。
在实现本发明的过程中，发明人提供了一种改性激光诱导石墨烯材料的制备方法，该方法通过激光将含有纤维素和前驱体的基材层转化激光诱导石墨烯。发明人通过大量研究发现，对前驱体的改性包括进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酯化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚等多种化学反应，可以增强前驱体的耐温和成炭性能。将阻燃基团接枝至前驱体上，提高前驱体的耐高温性能。同时在进行激光诱导转化的过程中，还需要合理的设置激光参数，使得激光深入基材层内部，将前驱体转化为激光诱导石墨烯，同时激光还不破坏基材层中的纤维素，维持基材层的稳定以及基材层与激光诱导石墨烯的连接，从而使得制得的激诱导石墨烯更好的附着于基材层的表面，解决石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。该制备方法使用的激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。可以使用的激光的波长范围可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。LIG基材表面承受的激光强度需要＞3J/cm2。
在实现本发明的过程中，发明人还提供了一种改性激光诱导石墨烯材料，该改性激光诱导石墨烯材料包括基材层、石墨烯功能层。石墨烯功能层含有激光诱导石墨烯组分。基材层还含有改性前驱体，改性前驱体连接/接枝了阻燃基团，前驱体还可以连接环氧基团、酯类基团。改性激光诱导石墨烯材料中含有纤维素，纤维素分散于基材层与石墨烯功能层。在改性激光诱导石墨烯材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素分子互相缠结形成网状结构，部分激光诱导石墨烯组分嵌套于该网状结构中。改性激光诱导石墨烯材料因其具备的特殊结构，克服了石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。改性激光诱导石墨烯材料具有改性前驱体，因而具有了更好的耐温、防水、以及柔韧性能。
发明人提供的石墨烯层状复合材料可应用于柔性传感器、智能加热装置、纳米摩擦发电机、自清洁过滤器、超级电容等领域。
实施例1.一种石墨烯层状复合材料的制备方法，其中，使用激光照射LIG基材制备石墨烯层状复合材料，所述激光的波长范围是9.3-10.6μm、625-740nm、450-480nm、1053nm，基材表面承受的激光强度范围是3J/cm2-40J/cm2，所述LIG基材含有纤维素和前驱体，所述LIG基材的厚度是0.02-0.5mm。
实施例2.根据实施例1所述的制备方法，其中，所述纤维素的直径＞100nm、长径比是1000-1500；或者所述纤维素直径是0.1-120um、长度是0.5-5mm。
实施例3.根据实施例1-2所述的制备方法，其中，所述前驱体是木质素，所述木质素的粒径是10nm-500nm。
实施例4.根据实施例1-3所述的制备方法，其中，所述木质素添加量是0-41％。
实施例5.根据实施例1-4所述的制备方法，其中，所述木质素添加量为29％。
实施例6.根据实施例1-5所述的制备方法，其中，激光强度范围是5.5-20J/cm2。
实施例7.根据实施例1-6所述的制备方法，其中，所述前驱体包括生物质类材料、合成类材料、矿物类材料。
实施例8.根据实施例1-7所述的制备方法，其中，前驱体是生物质类材料，生物质类材料的成分包括木质素、单宁酸、多酚、黄酮类化合物。
实施例9.根据实施例1-8所述的制备方法，其中，木质素包括Kraft木质素、碱木质素、脱碱木质素。
实施例10.根据实施例1-9所述的制备方法，其中，合成类材料包括光刻胶、聚酰亚胺膜、聚酰亚胺纤维纸、聚酰亚胺泡沫海绵、聚砜类聚合物、特氟龙、酚醛树脂、ABS塑料、聚苯乙烯聚合物；矿物类材料包括煤炭、炭黑、氧化石墨烯、石墨。
实施例11.根据实施例1-10所述的制备方法，其中，激光由激光器产生，激光器是CO2源激光器、蓝光器、飞秒激光器的一种。
实施例12.根据实施例1-11所述的制备方法，其中，激光器的功率范围是0-50W。
实施例13.根据实施例1-12所述的制备方法，其中，LIG基材处于保护气的环境中，保护气可以是还原性和惰性气体。
实施例14.根据实施例1-13所述的制备方法，其中，保护气是H2、Ar、N2、SF6或几种气体的混合气体。
实施例15.一种层状激光诱导石墨烯基材的制备方法，包括如下步骤：
S001.将前驱体与纤维素进行混合，制得基材浆料；所述前驱体包括石油基材料、生物基材料，所述石油及材料包括氧化石墨烯、聚酰亚胺，所述生物基材料包括木质素、茶多酚、单宁酸；
S002.将所述浆料进行热压成型，制得LIG基材，LIG基材的厚度是0.02-0.5mm。
实施例16.一种层状激光诱导石墨烯基材的制备方法，包括如下步骤：
S001.制备附着液，附着液含有前驱体，所述前驱体包括石油基材料、生物基材料，所述石油及材料包括氧化石墨烯、聚酰亚胺，所述生物基材料包括木质素、茶多酚、单宁酸；
S002.使附着液附着于LIG基材，LIG基材含有纤维素，所述附着的方法可以浸渍、涂覆、喷涂；
S003.将附着了附着液的LIG基材干燥，制得含有前驱体的LIG基材，所述LIG基材的厚度是0.02-0.5mm。
实施例17.根据实施例1-16所述的制备方法，其中，所述混合方法包括搅拌、超声、乳化；所述制备方法还包括，使用流延法或真空抽滤法将纤维素增强的原料制备成纤维素增强的基材浆料湿膜；使用热压成型方法所述基材浆料湿膜固化成为纤维素增强的薄层基材。
实施例18.根据实施例1-17所述的制备方法，其中，热压成型的温度40-150℃，压力1-15MPa。
实施例19.根据实施例1-18所述的制备方法，其中，热压成型的温度为50-100℃，压力为5-10MPa。
在一些实施例中，石墨烯层状复合材料的制备过程中，在LIG基材中加入一定量的纤维素，同时控制激光的功率与波长，使得进入石墨烯功能层的部分纤维素转变为了碳化纤维素，且部分纤维素与碳化纤维素分子互相缠结形成网状结构，并使得部分激光诱导石墨烯组分嵌套于该网状结构中。这些纤维素会更牢靠的连接基材层与石墨烯功能层，克服了石墨烯功能层与基材层结合不牢靠的问题，使得石墨烯与基材可以结合牢靠不易脱落，并实现了优异的柔性、耐候性等特点。
另外在一些实施例中，通过合理的设置LIG基材中的前驱体添加量，使得前驱体更好的包裹纤维素，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的激光诱导石墨烯更好的附着于基材层表面。
附图说明
图1激光功率1.25W在添加纤维素LIG基材(左)与未添加纤维素LIG基材(右)激光诱导石墨烯电镜图
图2激光功率1.5W在添加纤维素LIG基材(左)与未添加纤维素LIG基材(右)激光诱导石墨烯电镜图
图3木质素纤维素LIG基材制得的LIG的SEM图
图4木质素纤维素LIG基材制得的LIG的TEM图
图5木质素纤维素LIG基材制得的LIG的XRD特征峰
图6木质素纤维素LIG基材制得的LIG的拉曼特征峰
图7木质素纤维素LIG基材制得的LIG的XPS图谱
图8卷对卷制备LIG工艺示意图
图9石墨烯层状复合材料示意图
图10含有纤维素的石墨烯层状复合材料示意图
图11纯纤维素纸(左)、木质素纤维素复合纸(中)和基于木质素纤维素复合纸制备的LIG(右)的SEM图
图12木质素纤维素LIG基材(左)、基于木质素纤维素LIG基材进行1次扫描(中)、基于木质素纤维素LIG基材进行2次扫描(右)的SEM图
图13基于木质素纤维素LIG基材制备LIG的过程示意图
图14基于木质素纤维素LIG基材制备LIG的SEM图(不同激光强度，(a)50wt％,(b)60wt％,(c)70wt％,(d)80wt％，全功率为40W)
图15基于木质素纤维素LIG基材制备的LIG的TEM图
图16基于木质素纤维素LIG基材制备的LIG的TEM图(不同木质素添加量，(a,b)2wt％,(c,d)9wt％,(e,f)15wt％,(g,h)21wt％,(i,j)34wt％)
图17激光诱导石墨烯嵌套于纤维素与碳化纤维素结构的示意图
图18实施例中超级电容器的结构示意图
图19实施例中应变传感器的结构示意图
图20实施例中焦耳加热器的结构示意图
图21实施例中气体传感器的结构示意图
图22实施例中石墨烯超级电容器外观示意图
图23实施例中包含两层石墨烯复合材料的超级电容器示意图
图24实施例中包含单层石墨烯复合材料的超级电容器示意图
图25实施例中石墨烯超级电容器的结构示意图
图26实施例中提供的内部并联的石墨烯超级电容器的结构示意图
图27实施例中提供的一种石墨烯应变传感器的制备流程示意图
图28实施例中提供的一种石墨烯应变传感器的结构示意图
图29实施例中提供的一种石墨烯气体传感器的组成结构示意图
图30实施例中提供的一种应用气体检测原理流程示意图
图31基于制浆、造纸和激光划片工艺的潜在卷到卷LIG电极制造工艺示意图
图32木质素的环氧化和丙烯酸酯化过程示意图
图33FeNi3纳米粒子与其氧化物(Fe3O4)在LIG基质中以形成的多层结构示意图
图34氮掺杂激光诱导石墨烯示结构示意图
图中：100-基材层；200-石墨烯功能层；210-激光诱导石墨烯；310-木质素溶液；320-改性溶液；330-纤维素；340-碳化纤维素；410-第一辊单元；420-第二辊单元；430-第三辊单元；510-第一激光器；520-第二激光器；600-芯子；601-正集流体；602-负集流体；603-密封塞；604-吸液式隔膜；605-内极耳；606-外极耳；607-石墨烯电极；608-电解液；609-外包装；610-电容器本体；611-塑化层；612-应力缓冲层。
具体实施方式
术语解释
石墨烯：石墨烯(Graphene)是一种以sp2杂化连接的碳原子紧密堆积成单层二维蜂窝状晶格结构的新材料。
激光诱导石墨烯：激光诱导石墨烯(LIG)是一种以sp2杂化连接的碳原子紧密堆积成的多层(通常为五层以上)的三维蜂窝状晶格结构的多孔新材料。
前驱体：前驱体也叫LIG前驱体，是生成激光诱导石墨烯的前体材料。
纤维素层状材料：以纤维素或纳米纤维素，或其混合物制备的
激光诱导石墨烯基材：激光诱导石墨烯基材也叫LIG基材，是用于激光法制备激光诱导石墨烯的基材。
掺杂物质：铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质、硫化合物等可引入激光诱导石墨烯基材，提升激光诱导石墨烯材料相关性能的物质。
杂化物：是指掺杂物质的一种或其组合在加入LIG基材后，在激光扫描后生成的物质(含功能基团)。
基础方案1
本发明的一个实施例提供了一种柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
基材层含有纤维素，还包含一种或多种其他容易被激光诱导石墨化的前驱体，如生物基材料，包括纸张、纺织品，所述纺织品可以是丝绸、棉麻等；合成类材料，包括光刻胶、聚酰亚胺(PI)、PI纤维纸、PI泡沫海绵、聚砜类聚合物(如PES等)、特氟龙(如PTFE、FEP、PFA、ETFE)、酚醛树脂、ABS塑料、聚苯乙烯系聚合物等；矿物类材料，包括煤炭、炭黑、氧化石墨烯(GO)、石墨。
本发明的一个实施例中，基材层中前驱体的比例是2wt％-40wt％，优选的比例是10wt％-30wt％。基层中的前驱体类型可以是生物基材料，优选的生物基材料是木质素，木质素的粒径是10nm-500nm。基层中的纤维素直径＞1000nm，不同木质素添加量的TEM结果如图16所示。
激光诱导石墨烯的生产方法是使用激光辐射含碳的前驱体，在前驱体表面产生局部的瞬间高温(＞1000℃)，使碳原子完成由sp3到sp2的杂化，形成具有蜂窝状结构的3D多孔石墨烯。在激光扫描过程中，除碳碳单键外，碳氢、碳氧、碳碳双化合键等被破坏，碳前驱体中除碳以外的元素也会在高温下挥发(空气氛围中)。前驱体中的纤维素在适当强度的激光照射下，可以被石墨化而不会被高温破坏分解，这样就会形成碳化纤维素，维持纤维素特有的束管结构，纤维素(包括碳化纤维素)可以在激光扫描后仍然维持网状骨架结构。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的激光诱导石墨烯更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的碳源层过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。
基础方案2
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
优选的方案1
本发明的一个实施例提供了一种优选的生物基的柔性的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。基材层中包括前驱体。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。前驱体粒径是10nm-500nm。纤维素直径＞1000nm。优选的前驱体可以是木质素，还可以是氧化石墨烯、聚酰亚胺。
本发明的一个实施例中，石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。
优选的方案2
本发明的一个实施例中，本发明提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。
本发明的一个实施例中，基材层包含前驱体，前驱体可以是生物质类材料，包括纸张、纺织品，所述纺织品可以是丝绸、棉麻等。生物质类材料的包括木质素(Kraft木质素、碱木质素、脱碱木质素等)、纤维素、单宁酸、多酚(如茶多酚、绿原酸、苹果多酚、可可多酚、白藜芦醇等)、黄酮类化合物(如黄酮醇、花青素、类黄酮等)。使用生物质类材料具有环境友好性、可降解等诸多优点。
本发明的一个实施例中，木质素的粒径可以是纳米级别的，如纳米木质素颗粒，其粒径范围在50-500nm，可以作为更好的孔隙填充物，用于占据中间的纳米级孔隙。
优选的方案3
本发明的一个实施例提供了一种改性激光诱导石墨烯基材制备方法，具体的步骤包括：
S001.前驱体改性，其方法包括如下步骤，
(1)前驱体改性，对前驱体的改性包括进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酯化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚等多种化学反应，增强前驱体的耐温和成炭性能。改性主要是发生在前驱体中的酚羟基上。进一步的前驱体连接有环氧基团、酯类基团。
进一步的，前驱体改性步骤中，将前驱体进行接枝和酯化，通过化学催化的方法将环氧基团接枝至前驱体的酚羟基上，随后与丙烯酸产生酯化反应制备环氧前驱体丙烯酸酯溶液，以提高前驱体的粘性和高温下的流延性。
S002.纤维素增强的改性前驱体LIG基材制备，其方法包括如下步骤，
(1)前驱体与纤维素混合液制备，将纤维素或纳米纤维素加入前驱体溶液中，搅拌、超声、乳化后制成前驱体纤维素混合溶液。前驱体添加量是0-41wt％，优选的前驱体添加量为29wt％。改性前驱体/纤维素添加量，改性前驱体添加量：0-34wt％，优选的改性前驱体添加量21wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将前驱体与纤维素混合液制备成前驱体纤维素湿膜。
(3)热压成型，前驱体纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为前驱体纤维素LIG基材，优选的温度为50-110℃，优选的压力为5-10MPa。
S004.设置激光加工参数对LIG基材进行激光照射,其方法包括如下步骤，
激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域。
通过对LIG基材中前驱体的改性，可以提高其制备的激光诱导石墨烯的品质，如提高激光诱导石墨烯的导电性、疏水性等。通过对LIG基材中前驱体的改性，还可以提高LIG基材的强度、柔韧性能。
优选的方案4
本发明的一个实施例提供了一种掺杂石墨烯材料的制备方法，该方法为激光诱导的方法将LIG基材转化为激光诱导石墨烯，LIG基材可以进行掺杂，如掺杂铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质、硫化合物等。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。LIG基材中含有纤维素。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)对LIG基材进行掺杂。可选的掺杂物质包括铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质、硫化合物等。铁系元素化合物包括氯化铁、硝酸铁、氯化镍、硝酸镍、氯化钴、硝酸钴；锰化合物包括氧化锰；氮化合物包括尿素、三聚氰胺；硼化合物包括硼酸、硼酸盐；磷化合物包括磷酸、磷酸盐；金化合物包括四氯金酸、氰金酸钾；银化合物包括银氧化物、银氢氧化物、银硫化物、银硫酸盐、银卤化物、银硝酸盐。掺杂的方法可以是直接在LIG基材原料中直接混合掺杂物质，还可以是通过喷涂、浸渍、沉积等方法在LIG基材表面附着这些掺杂物质。
(3)设置激光加工参数对LIG基材进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
掺杂了铁系元素化合物、锰化合物的激光诱导石墨烯可用于超级电容的电极，这种电极在储电的过程中，这些掺杂的铁系元素化合物、锰化合物会发生化学反应，使得电容形成赝电容，提高超级电容的电容量。
掺杂了氮化合物、硼化合物、硼单质、磷化合物的激光诱导石墨烯，这些掺杂的化合物可以增强激光诱导石墨烯的半导体性能，如降低其面电阻。
掺杂了金化合物、银化合物、金单质、银单质的激光诱导石墨烯，这些掺杂的化合物作为导电剂可以直接降低激光诱导石墨烯的电阻。
实施例1
本发明的一个实施例提供了一种柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分激光诱导石墨烯嵌套于该网状结构中。
本发明的一个实施例中，石墨烯功能层中的石墨烯与激光诱导石墨烯的比例是1:1-1:2，激光诱导石墨烯的拉曼光谱中，IG/ID为0.5-5.0，I2D/IG为0.1-1.0，La为10-40mm。石墨烯功能层的面电阻为2-33000Ω/square，Ω/square同Ω/cm2。石墨烯功能层的导电率为8-5500S/cm。石墨烯功能层的比表面积为10-350m2/g。石墨烯功能层的孔径为0-750nm。石墨烯功能层的厚度为0.05-350μm。石墨烯与激光诱导石墨烯比例的检测方法是TEM检测。基材层的厚度是0.02-0.5mm。
实施例2
本发明的一个实施例提供了一种柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。
本发明的一个实施例中，石墨烯功能层中的石墨烯与激光诱导石墨烯的比例是1:1-1:2，石墨烯与激光诱导石墨烯比例的检测方法是TEM检测。拉曼光谱中，IG/ID为1.0-3.3，I2D/IG为0.4-0.8，La为20-45mm。石墨烯功能层的面电阻为18-150Ω/square。石墨烯功能层的导电率为50-200S/cm。石墨烯功能层的比表面积为10-350m2/g。石墨烯功能层的孔径为0-750nm。石墨烯功能层的厚度为0.05-35μm。石墨烯功能层的C相对含量为85wt％-93wt％、O相对含量为5wt％-10wt％、N相对含量为2wt％-5wt％，如图3至图7所示。
本发明的一个实施例中，基材层可以是纤维素增强的聚酰亚胺，其中纤维素与聚酰亚胺的质量比为4:1。纤维素在基材层中形成相互交错的网状结构，聚酰亚胺附着在纤维素的纤维表面，在基材层制备过程中液态的聚酰亚胺还可以渗入到纤维素的纤维表面，聚酰亚胺固化后纤维素增强的聚酰亚胺纤维纸相较于聚酰亚胺膜具有更大的自由空间/孔隙。聚酰亚胺纤维纸基材层的透气率为1700-2200mL·mm·(cm2·h·mmAq)-1。聚酰亚胺纤维纸的抗张指数：＞40N·m/g，撕裂指数：＞30mM·m2/g，电常数：1.5-2.0，介质损耗因数：3.1×10-3-6.5×10-3。
实施例3
本发明的一个实施例提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。基材包括木质素和纤维素。石墨烯功能层的拉曼光谱中，IG/ID为0.5-3.4，I2D/IG为0.2-0.8，La为10-40mm。
本发明的一个实施例中，基材层是木质素纤维素共混复合纸：拉伸强度30-130MPa，接触角30-80°。木质素纤维素共混复合纸的激光诱导石墨烯IG/ID0.5-3.0，I2D/IG0.1-1.0，La25-150mm，面电阻2-20Ω/square。
本发明的一个实施例中，基材层是木质素纳米纤维素共混复合纸：拉伸强度50-250MPa，接触角50-90°。木质素纳米纤维素共混复合纸激光诱导石墨烯的IG/ID 0.5-3.0，I2D/IG 0.1-0.8，La 25-150mm，面电阻5-50Ω/square。
本发明的一个实施例中，纳米纤维素可以增强复合纸的机械强度和表面疏水性，但由于纳米纤维素直径较小、长度较短，所形成的复合纸表面较为光滑，孔隙率较小且多为微孔，导致激光难以穿透，能量(热量)无法均匀有效地传导至复合纸内部，会阻碍木质素的石墨化，导致能量消耗高且形成的LIG电阻较高。
实施例4
本发明的一个实施例提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。基材包括木质素和纤维素。基材层通过100MPa，温度100℃的热压处理。通过激光对基材层进行扫描，激光扫描速度是175mm/s，激光强度是32W，激光焦距为0，即聚焦于基材层表面。基材层中的纤维素直径在15-30um，木质素粒径>500nm。如图1至图2所示。
表1含有纤维素与木质素基材层的及LIG参数
纳米纤维素可以增强复合纸的机械强度和表面疏水性，但由于纳米纤维素直径较小、长度较短，所形成的的复合纸表面较为光滑，孔隙率较小且多为微孔，导致激光难以穿透，能量(热量)无法均匀有效地传导至复合纸内部，会阻碍木质素的石墨化，导致能量消耗高且形成的LIG电阻较高。
纤维素的直径还会影响基材层的机械强度，以及防水性能(接触角)。基材层中添加纤维素是纳米纤维素，纳米纤维素直径<100nm，木质素粒径>500nm。基材层通过100MPa，温度100℃的热压处理，其机械拉伸强度及接触角情况如下。
表2含有纤维素及不同木质素添加量基材层参数

基材层添加纳米纤维素可以增强基材层的机械拉伸强度，并且提高基材层的疏水性能。
实施例5
本发明的一个实施例提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。基材层包括纤维素和纳米木质素。纳米木质素可以显著的提高激光诱导石墨烯品质，同时纳米木质素的粒径越小，激光诱导石墨烯的品质越好。
表3含有纤维素及不同纳米木质素粒径基材层参数
纳米木质素可以更好的包裹于纤维素表面，保护纳米纤维素在激光照射过程中不被分解。同时纳米木质素转变为激光诱导石墨烯。从而提高石墨烯功能层品质。
实施例6
本发明的一个实施例提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。基材层中不同直径的纤维素对激光诱导石墨烯的品质有影响。经发明人大量研究发现，添加普通纤维素的基材层所制备的激光诱导石墨烯品质，优于添加纳米纤维素进基材层所制备的激光诱导石墨烯的品质。因此可以使用普通纤维素作为提升基材层的添加剂，提升激光诱导石墨烯的品质，同时还可以降低成本。
表4含有不同纤维素直径及纳米木质素基材层参数
实施例7
本发明的一个实施例提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。
本发明的一个实施例中，一种基材层包括纤维素和单宁酸。基材层通过100MPa，温度100℃的热压处理。通过激光对基材层进行扫描，激光扫描速度是175mm/s，激光强度是32W，激光焦距为0，即聚焦于基材层表面。基材层及石墨烯功能层的性能参数如下。
表5含有纤维素及单宁酸基材层参数
本发明的一个实施例中，一种基材层包括纤维素和茶多酚。基材层通过100MPa，温度100℃的热压处理。通过激光对基材层进行扫描，激光扫描速度是175mm/s，激光强度是32W，激光焦距为0，即聚焦于基材层表面。基材层及石墨烯功能层的性能参数如下。
表6含有纤维素及茶多酚基材层参数
石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。
实施例8
本发明的一个实施例提供了一种掺杂激光石墨烯材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分激光诱导石墨烯嵌套于该网状结构中。石墨烯功能层还含有杂化物，杂化物包括铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等，以及上述物质的组合。
本发明的一个实施例中，石墨烯功能层中的石墨烯与激光诱导石墨烯的比例是1:1-1:2，激光诱导石墨烯的拉曼光谱中，IG/ID为0.5-5.0，I2D/IG为0.1-1.0，La为10-40mm。石墨烯功能层的面电阻为2-33000Ω/square，Ω/square同Ω/cm2。石墨烯功能层的导电率为8-5500S/cm。石墨烯功能层的比表面积为10-350m2/g。石墨烯功能层的孔径为0-750nm。石墨烯功能层的厚度为0.05-350μm。石墨烯与激光诱导石墨烯比例的检测方法是TEM检测。基材层的厚度是0.02-0.5mm。
实施例9
本发明的一个实施例提供了一种改性激光诱导石墨烯材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在改性激光诱导石墨烯材料的结构中，部分激光诱导石墨烯嵌套于该网状结构中。基材层还含有改性前驱体，进一步的改性前驱体连接/接枝了阻燃基团，阻燃基团包括卤素基团、磷系基团。进一步的前驱体连接有环氧基团、酯类基团。
本发明的一个实施例中，石墨烯功能层中的石墨烯与激光诱导石墨烯的比例是1:1-1:2，激光诱导石墨烯的拉曼光谱中，IG/ID为0.5-5.0，I2D/IG为0.1-1.0，La为10-40mm。石墨烯功能层的面电阻为2-33000Ω/square，Ω/square同Ω/cm2。石墨烯功能层的导电率为8-5500S/cm。石墨烯功能层的比表面积为10-350m2/g。石墨烯功能层的孔径为0-750nm。石墨烯功能层的厚度为0.05-350μm。石墨烯与激光诱导石墨烯比例的检测方法是TEM检测。基材层的厚度是0.02-0.5mm。
实施例10
本发明的一个实施例提供了一种应用了石墨烯层状复合材料的力学传感器，力学传感器在外力作用下变形，会间接改变内部LIG材料的分布和接触状态，从而导致LIG电阻的有规律变化，可用于检测拉力和压力的电信号变化。
石墨烯层状复合材料的力学传感器包括基于石墨烯电极、石墨烯叉指电极、塑封膜。
进一步的，石墨烯层状复合材料的力学传感器包括基于PI纤维膜的LIG圆片电极、基于牛皮纸的LIG叉指电极、塑封膜。
石墨烯层状复合材料的力学传感器可用于实时监测人体状态，如人体压力分布显示、枕头压力分布、睡姿监测及判断、坐姿监测及判断、足底压力等方向。其输出电阻或电压随着传感器应变的增大而增加，通过特定的应变-电阻/电压关系，并结合相关算法，可广泛运用于智能可穿戴设备、人机交互、医疗康复等不同领域。
实施例11
本发明的一个实施例提供了一种应用了石墨烯层状复合材料的传感器系统，包括信号放大器、LCR功能单片机、蓝牙通讯模块。传感器感受到力学变化后，将相应的电信号传输到信号放大器，经信号放大后，传输至单片机，由单片机进行数据收集、处理和读取，再通过蓝牙通信模式传至手机，由微信小程序进行数据点绘图并呈现。
实施例12
本发明的一个实施例提供了一种应用石墨烯层状复合材料的电化学传感器的传感器材料。石墨烯通过与被测物体等发生反应并产生与反应物浓度成正比的电信号来工作，可用于湿度、温度、气体、液体、化学物质等检测。
本发明的一个实施例提供了一种超级电容的电极材料及超级电容。电极材料中含有生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。激光诱导石墨烯用于储存电荷，可以提高超级电容的能量密度、循环寿命，并可以降低制造成本。
实施例13
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，该方法通过激光将含有纤维素的LIG基材转化石墨烯，如图11所示。具体的实施为设置激光加工参数对LIG基材表面进行激光照射，使前驱体转变为石墨烯。
本发明的一个实施例中，激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射基材的相同区域，如图12所示。LIG基材中包含纤维素成分。
LIG基材包含前驱体，前驱体可以是生物质类材料，包括纸张、纺织品，所述纺织品可以是丝绸、棉麻等。生物质类材料的包括木质素(Kraft木质素、碱木质素、脱碱木质素等)、纤维素、单宁酸、多酚(如茶多酚、绿原酸、苹果多酚、可可多酚、白藜芦醇等)、黄酮类化合物(如黄酮醇、花青素、类黄酮等)。使用生物质类材料具有环境友好性、可降解等诸多优点。
纤维素则属于半刚性分子，其分子链柔顺且纤维素聚合度高、分子取向度好、化学稳定性强。在LIG基材中加入纤维素，可利用纤维素的属于半刚性分子的优点，在复合体系中形成网状结构，使LIG基材具有较大的自由空间/孔隙。激光束在照射至LIG基材表面时，更容易深入纸张内部，可使纸张吸收更多的热量且热量分布更均匀。纤维素独特的孔隙结构可引导石墨烯在纸张表面生长时能更好地填充纸张的自由空间，均匀地分布在纸张表面，而不是垂直向下生长(分布杂乱无序)。此时形成的石墨烯功能层表面更光滑、平整，裂纹较少。一般在激光扫描下，基材很容易受高温影响而发生扭曲甚至断裂，导致石墨烯功能层极易从基材上脱落；相比之下，由于纤维素分子有极性，分子链之间相互作用力很强，不易发生严重的形状扭曲，能牢固抓紧纸张表层生长的石墨烯，改善石墨烯复合材料的整体机械稳定性，不同木质素添加量TEM图如图16所示。
实施例14
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，该方法通过激光将含有纤维素的LIG基材转化石墨烯。具体的步骤包括：
S001.木质素提纯，木质素提纯的方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸等无机酸。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)水洗与烘干，对木质素进行水洗和烘干处理。
S002.纤维素增强的含木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，将木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，在木质素纤维素LIG基材表面生成石墨烯功能层。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射基材的相同区域，如图12所示。基材中包含纤维素成分。
纳米纤维素可以增强复合纸的机械强度和表面疏水性，但由于纳米纤维素直径较小、长度较短，所形成的的复合纸表面较为光滑，孔隙率较小且多为微孔，导致激光难以穿透，能量(热量)无法均匀有效地传导至复合纸内部，会阻碍木质素的石墨化，导致能量消耗高且形成的LIG电阻较高。
基材层添加纳米纤维素可以增强基材层的机械拉伸强度，并且提高基材层的疏水性能。
纳米木质素可以更好的包裹于纤维素表面，保护纳米纤维素在激光照射过程中不被分解。同时纳米木质素转变为激光诱导石墨烯。从而提高石墨烯功能层品质。
由于木质素是刚性大分子，硬度高但略显脆性；而纤维素则属于半刚性分子，尽管强度较差，但其分子链柔顺性要优于木质素，且纤维素聚合度高、分子取向度好、化学稳定性强。在木质素中加入纤维素，可结合两者的优点(硬度和柔性)，在复合体系中形成网状结构，使木质素复合纸具有较大的自由空间/孔隙。激光束在照射至复合纸表面时，更容易深入纸张内部，可使纸张吸收更多的热量且热量分布更均匀。纤维素独特的孔隙结构可引导石墨烯在纸张表面生长时能更好地填充纸张的自由空间，均匀地分布在纸张表面，而不是垂直向下生长(分布杂乱无序)。此时形成的LIG表面更光滑、平整，裂纹较少。一般在激光扫描下，木质素很容易受高温影响而发生扭曲甚至断裂，导致激光诱导石墨烯极易从基材层上脱落；相比之下，由于纤维素分子有极性，分子链之间相互作用力很强，不易发生严重的形状扭曲，能牢固抓紧纸张表层生长的石墨烯，改善石墨烯复合材料的整体机械稳定性。
实施例15
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，该方法通过激光将含有纤维素的LIG基材转化石墨烯。具体的步骤包括：
S001.木质素提纯，木质素提纯的方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)水洗与烘干，对木质素进行水洗和烘干处理。
S002.纤维素增强的含木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将常规纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材表面生成激光诱导石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射基材的相同区域。基材中包含纤维素成分。
表7木质素添加普通纤维素与纳米纤维素对比
在LIG基材中添加常规纤维素，即直径、长度较大的纤维素，常规纤维素纤维更粗，在LIG基材中形成孔隙较大，可以更好的让激光穿透至更深层次的LIG基材中，进而形成品质更高的LIG，其面电阻更低。在LIG基材中添加纳米纤维素，即尺寸更小的纤维素，这些尺寸更小的纤维素可以使得石墨烯复合材料更加致密，提高其拉伸强度、防水性能等。
实施例16
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.LIG基材制备，其方法包括如下步骤，
(1)使用木质素溶液浸渍纤维素层状材料，制备LIG基材，LIG基材含有纤维素；木质素溶液的木质素质量百分数为2wt％-25wt％。
(2)使用热压固化的方法，使得浸渍有木质素溶液的LIG基材干燥固化。固化温度40-150℃、1-15MPa；优选的温度为50-100℃，优选的压力为5-10MPa。
S002.激光诱导扫描，
使用激光照射浸渍了木质素的LIG基材，使LIG基材表面生成激光诱导石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是8-50J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。
由于木质素是刚性大分子，硬度高但略显脆性；而纤维素则属于半刚性分子，尽管强度较差，但其分子链柔顺性要优于木质素，且纤维素聚合度高、分子取向度好、化学稳定性强。在含有纤维素的基材中引入木质素，可结合两者的优点(硬度和柔性)，在复合体系中形成网状结构，使基材具有较大的自由空间/孔隙。激光束在照射至LIG基材表面时，更容易深入纸张内部，使LIG基材吸收更多的热量且热量分布更均匀。纤维素独特的孔隙结构可引导石墨烯在纸张表面生长时能更好地填充纸张的自由空间，均匀地分布在纸张表面，而不是垂直向下生长(分布杂乱无序)。此时形成的石墨烯功能层表面更光滑、平整，裂纹较少。一般在激光扫描下，木质素很容易受高温影响而发生扭曲甚至断裂，导致激光诱导石墨烯极易脱落；相比之下，由于纤维素分子有极性，分子链之间相互作用力很强，不易发生严重的形状扭曲，能牢固抓紧纸张表层生长的石墨烯，改善石墨烯复合材料的整体机械稳定性。
实施例17
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.木质素提纯与改性，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
(5)木质素改性，对木质素的改性包括进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酞化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚等多种化学反应，增强木质素的耐温和成炭性能。
进一步的，木质素改性步骤中，将木质素进行接枝和酯化，通过化学催化的方法将环氧基团接枝至木质素的酚羟基上，随后与丙烯酸产生酯化反应制备环氧木质素丙烯酸酯溶液，以提高木质素的粘性和高温下的流延性。
S002.纤维素增强的改性木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。改性木质素/纤维素添加量，改性木质素添加量：0-34wt％，优选的改性木质素添加量21wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-110℃，优选的压力为5-10MPa。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。激光器的功率范围是5-30W，照射功率可以是10％、20％、30％、40％、50％、60％、70％、80％、90％、100％。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域，LIG基材中包含纤维素成分。
实施例18
本发明的一个实施例提供了一种改性激光诱导石墨烯基材制备方法，具体的步骤包括：
S001.前驱体改性，其方法包括如下步骤，
(1)前驱体改性，进一步的，前驱体改性步骤中，将阻燃基团接枝至前驱体上，阻燃基团包括卤素基团、磷系基团。阻燃基团物质占前驱体与的质量比是0-10wt％，进一步的阻燃基团物质占前驱体与的质量比是3-8wt％，
S002.纤维素增强的改性前驱体LIG基材制备，其方法包括如下步骤，
(1)前驱体与纤维素混合液制备，将纤维素或纳米纤维素加入前驱体溶液中，搅拌、超声、乳化后制成前驱体纤维素混合溶液。前驱体添加量是0-41wt％，优选的前驱体添加量为29wt％。改性前驱体/纤维素添加量，改性前驱体添加量：0-34wt％，优选的改性前驱体添加量21wt％。优选的纤维素直径是＞1000nm。前驱体可以是木质素、单宁酸、茶多酚等。
(2)铺膜，通过流延法或真空抽滤法将前驱体与纤维素混合液制备成前驱体纤维素湿膜。
(3)热压成型，前驱体纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为前驱体纤维素LIG基材，优选的温度为50-110℃，优选的压力为5-10MPa。
S004.设置激光加工参数对LIG基材进行激光照射,其方法包括如下步骤，
激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域。
通过对LIG基材中前驱体的改性，可以提高其制备的激光诱导石墨烯的品质，如提高激光诱导石墨烯的导电性、疏水性等。通过对LIG基材中前驱体的改性，还可以提高LIG基材的强度、柔韧性能。
实施例19
本发明的一个实施例提供了一种改性激光诱导石墨烯基材制备方法，激光石墨烯前驱体是木质素，具体的步骤包括：
S001.木质素提纯与改性，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，获得有机溶剂可溶的木质素。通过有机溶剂萃取和分级可以控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
在100ml丙酮中加入10g木质素，在室温下搅拌60分钟，搅拌后在冰浴中超声60分钟，萃取木质素中的可溶成分。接下来使用真空过滤，保留丙酮溶液。接下来通过旋转蒸发以除去丙酮，获取可溶于丙酮的木质素。
(4)水洗与烘干，对木质素进行水洗和烘干处理。使用水对获得的可溶于丙酮的木质素进行洗涤，接下来对这些可溶于丙酮木质素在50℃的真空烘箱中真空干燥。
按照相同的步骤，还可以使用乙醇或丁醇提取可溶于乙醇或丁醇的木质素。
S002.木质素改性，其方法包括如下步骤，
(5)木质素改性，对木质素的改性包括进行接枝和酯化反应，增强木质素的耐温和成炭性能。
进一步的，木质素改性步骤中，将木质素进行接枝和酯化，通过化学催化的方法将环氧基团接枝至木质素的酚羟基上，随后与丙烯酸产生酯化反应制备环氧木质素丙烯酸酯溶液，以提高木质素的粘性和高温下的流延性。
按照每1g木质素中分别添加0.5、1和2克环氧氯丙烷(ECH)的比例，将有机溶剂可溶木质素以1、3、5、10和20g的不同添加量溶于100mL的二甲基亚砜(DMSO)溶液中。随后在65℃下加入0.2克KOH溶液(30％，w/w)，搅拌混合2小时后，再次添加0.2gKOH，继续搅拌2小时。
冷却后，用0.5mol/L NaH2PO4·2H2O将溶液pH中和至7.5-8.0，最终通过缩水甘油化反应获得木质素基环氧树脂。
随后添加0.2对苯二酚0.2％吡啶，并在80℃下，按照每摩尔环氧基团添加0.9摩尔的丙烯酸的比例，在30分钟内加入加所需量的丙烯酸，最终获取木质素基环氧丙烯酸酯(LBEA)。
S003.纤维素增强的改性木质素LIG基材制备，其方法包括如下步骤，
(1)改性木质素与纤维素混合液制备，将纤维素粉碎并通过2mm筛子过筛，将2g过筛后的纤维素加入木质素基环氧丙烯酸酯混合体系中，在室温下以1000rpm搅拌过夜。通过8000rpm离心20分钟收集吸附有木质素基环氧丙烯酸酯的纤维素，用二甲基亚砜洗涤以去除未吸附的木质素基环氧丙烯酸酯，然后用水洗涤以去除二甲基亚砜。
(2)铺膜，将吸附有木质素基环氧丙烯酸酯的纤维素分散在200mL的去离子水中并均质化，直到获得均匀的悬浮液。通过真空抽滤将10ml悬浮液过滤至滤纸表面，获得湿态木质素纤维素复合纸。
(3)热压成型，将湿态木质素纤维素复合纸在室温下用5kg负载下加压10分钟，随后在100℃和5MPa下热压90分钟，获得改性LIG基材。改性LIG基材可以在50％的相对湿度(RH)、23℃下进行储藏。
S004.设置激光加工参数对LIG基材进行激光照射,其方法包括如下步骤，
激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域。
优选的，激光还可以是脉冲形式，脉冲持续时间为14μs，最大功率为40W，光栅横向速度为23in/s，焦距为35mm，激光束尺寸约为100μm。
优选的，激光扫描速率可以是其全速的30％，激光强度为全功率的50％、60％、70％和80％。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响改性激光诱导石墨烯材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
木质素基环氧丙烯酸酯(LBEA)是以木质素为原料，通过环氧树脂和丙烯酸合成，然后在DMSO体系中与纤维素形成良好交联，热压后得到高强度、柔韧、防水的复合纸。
实施例20
本发明的一个实施例提供了一种改性激光诱导石墨烯基材制备方法，激光石墨烯前驱体是木质素，具体的步骤包括：
S001.木质素提纯与改性，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
S002.木质素改性，其方法包括如下步骤，
(5)木质素改性，对木质素的改性包括进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酯化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚等多种化学反应，增强木质素的耐温和成炭性能。改性主要是发生在木质素中的酚羟基上。
进一步的，木质素改性步骤中，将木质素进行接枝和酯化，通过化学催化的方法将环氧基团接枝至木质素的酚羟基上，随后与丙烯酸产生酯化反应制备环氧木质素丙烯酸酯溶液，以提高木质素的粘性和高温下的流延性。
进一步的，木质素改性步骤中，将阻燃基团接枝至木质素上，阻燃基团包括卤素基团、磷系基团、硅系基团。
S003.纤维素增强的改性木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质素纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。改性木质素/纤维素添加量，改性木质素添加量：0-34wt％，优选的改性木质素添加量21wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-110℃，优选的压力为5-10MPa。
S004.设置激光加工参数对LIG基材进行激光照射,其方法包括如下步骤，
激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的 激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域。
通过对LIG基材中木质素的改性，可以提高其制备的激光诱导石墨烯的品质，如提高激光诱导石墨烯的导电性、疏水性等。通过对LIG基材中木质素的改性，还可以提高LIG基材的强度、柔韧性能。
实施例21
本发明的一个实施例提供了一种掺杂石墨烯材料的制备方法，具体的步骤包括：
S001.木质素提纯，包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
S002.纤维素增强的LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质素纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％，优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
(4)掺杂，对木质素纤维素LIG基材进行掺杂，通过喷涂、浸渍、沉积等方法将含有掺杂物质的掺杂剂附着于LIG基材。掺杂物质包括铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等。铁系元素化合物包括氯化铁、硝酸铁、氯化镍、硝酸镍、氯化钴、硝酸钴；锰化合物包括氧化锰；氮化合物包括尿素、三聚氰胺；硼化合物包括硼酸、硼酸盐；磷化合物包括磷酸、磷酸盐；金化合物包括四氯金酸、氰金酸钾；银化合物包括银氧化物、银氢氧化物、银硫化物、银硫酸盐、银卤化物、银硝酸盐。掺杂剂通过溶液的形式喷涂于LIG基材，还可以通过将LIG基材浸渍于掺杂剂的溶液中；溶液可以是含有掺杂物质的有机溶液、水溶液等，如乙醇溶液、丙酮溶液等。使用乙醇溶液、丙酮溶液这些易挥发物质作为溶剂，这些易挥发溶剂在掺杂过程后后迅速挥发，留下掺杂物质在LIG基材表面，便于后续的激光诱导石墨烯加工。还可以通过沉积的方法将这些掺杂物质附着于LIG基材表面。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。
本实施例所选用的激光器最大激光功率为10W，探头最大移动速度可达80mm/s。所加工器件性能最优状态的参数组合中功率设置为10％，探头移动速度设置为20-50mm/s。
实施例22
本发明的一个实施例提供了一种掺杂石墨烯材料的制备方法，具体的步骤包括：
S001.木质素提纯，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
S002.其他元素掺杂的LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质素纤维素混合溶液。木质素添加量是0-60wt％，优选的木质素添加量为10-40wt％。改性木质素/纤维素添加量，改性木质素添加量：0-34wt％，优选的改性木质素添加量50wt％。优选的纤维素直径是＞1500nm。
(2)木质素纤维素混合液中添加掺杂物质，掺杂物质包括铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等。铁系元素化合物包括氯化铁、硝酸铁、氯化镍、硝酸镍、氯化钴、硝酸钴；锰化合物包括氧化锰；氮化合物包括尿素、三聚氰胺；硼化合物包括硼酸、硼酸盐；磷化合物包括磷酸、磷酸盐；金化合物包括四氯金酸、氰金酸钾；银化合物包括银氧化物、银氢氧化物、银硫化物、银硫酸盐、银卤化物、银硝酸盐。
(3)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(4)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激 光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。
本实施例所选用的激光器最大激光功率为20W，探头最大移动速度可达80mm/s。所加工器件性能最优状态的参数组合中功率设置为10-30％，探头移动速度设置为10-30mm/s。进行掺杂可以进一步提高LIG产品的性能，如LIG的面电阻、IG/ID参数等。
实施例23
本发明的一个实施例提供了一种掺杂石墨烯材料的制备方法，该方法为激光诱导的方法将LIG基材转化为激光诱导石墨烯，LIG基材可以进行掺杂，掺杂铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。LIG基材中含有纤维素。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对LIG基材进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域。照射后得到激光诱导石墨烯复合材料。
(3)对激光诱导石墨烯复合材料进行掺杂。可选的掺杂物质包括铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等。铁系元素化合物包括氯化铁、硝酸铁、氯化镍、硝酸镍、氯化钴、硝酸钴；锰化合物包括氧化锰；氮化合物包括尿素、三聚氰胺；硼化合物包括硼酸、硼酸盐；磷化合物包括磷酸、磷酸盐；金化合物包括四氯金酸、氰金酸钾；银化合物包括银氧化物、银氢氧化物、银硫化物、银硫酸盐、银卤化物、银硝酸盐。掺杂的方法是通过喷涂、浸渍、沉积等方法在激光诱导石墨烯复合材料表面附着这些掺杂物质。
(4)设置激光加工参数对掺杂后的激光诱导石墨烯复合材料进行二次照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射激光诱导石墨烯复合材料的相同区域。照射后得到掺杂后的激光诱导石墨烯复合材料。
实施例24
本发明的一个实施例提供了一种掺杂石墨烯材料的制备方法，该方法为激光诱导的方法将LIG基材转化为激光诱导石墨烯，LIG基材可以进行掺杂，掺杂铁系元素化合物、锰化合物、氮化合物、硼化合物、硼单质、磷化合物、金化合物、银化合物、金单质、银单质等。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。LIG基材中含有纤维素。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。LIG基材还可以是热压牛皮纸。
(2)设置激光加工参数对LIG基材进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域。照射后得到激光诱导石墨烯复合材料。
(3)对激光诱导石墨烯复合材料进行掺杂。通过滴加、喷涂、浸渍的方式将掺杂剂附着于激光诱导石墨烯复合材料。掺杂剂中掺杂物质FeCl3：NiCl2的摩尔比为(0.5-1.5)：(0.5-1.5)，掺杂剂中的溶剂为乙醇或者丙酮。
(4)设置激光加工参数对掺杂后的激光诱导石墨烯复合材料进行二次照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射激光诱导石墨烯复合材料的相同区域。照射后得到掺杂后激光诱导石墨烯复合材料。优选的激光功率是全功率80W的5％，扫描速率是60mm/s。
通过本工艺制备的掺杂激光诱导石墨烯复合材料，其结构呈现“三明治”形式的多层结构，即“三明治”形式的掺杂激光诱导石墨烯复合材料包括基材层、石墨烯功能层、掺杂层、石墨烯功能层。
实施例25
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.制备含有纤维素与木质素的LIG基材层，LIG基材层的木质素含量为21wt％，木质素粒径＞500nm，纤维素直径15-30um。
S002.激光扫描LIG基材层，诱导LIG基材层表面生成为石墨烯功能层。使用的激光器为CO2激光器，激光强度为20-32W，激光移动速率为175mm/s，激光焦距为0。具体参数以及激光诱导石墨烯的参数如下表。
表8不同激光强度下激光诱导石墨烯参数对比
实施例26
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，该方法通过激光将含有纤维素的基材转化石墨烯。具体的步骤包括：
S001.制备含有纤维素与木质素的LIG基材，LIG基材的木质素含量为21wt％，木质素粒径＞500nm，纤维素直径15-30um。
S002.激光扫描LIG基材，诱导LIG基材表面转变为石墨烯功能层。使用的激光器为CO2激光器，激光强度为32W，激光移动速率为175mm/s，激光焦距为0.5-2.5mm。具体参数以及激光诱导石墨烯的参数如下表。
表9不同激光焦距下激光诱导石墨烯参数对比
实施例27
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.木质素提纯与改性，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
(5)木质素改性，对木质素的改性包括进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酞化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚等多种化学反应，增强木质素的耐温和成炭性能。
进一步的，木质素改性步骤中，将木质素进行接枝和酯化，通过化学催化的方法将环氧基团接枝至木质素的酚羟基上，随后与丙烯酸产生酯化反应制备环氧木质素丙烯酸酯溶液，以提高木质素的粘性和高温下的流延性。
S002.LIG基材制备与阻燃处理，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。改性木质素/纤维素添加量，改性木质素添加量：0-34wt％，优选的改性木质素添加量21wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
(4)阻燃处理，对木质素纤维素LIG基材表面喷涂阻燃剂，或者使用阻燃剂对木质素纤维素LIG基材进行浸润。阻燃剂可以是有机阻燃剂、无机阻燃剂，无机阻燃剂可以是氯化铁溶液、硝酸铁溶液、磷酸、硼酸等；还可以是卤系阻燃剂和非卤等阻燃剂，卤系阻燃剂可以是有机氯化物和有机溴化物。
对LIG基材进行阻燃处理之后，LIG基材具有阻燃效果、耐高温，提高LIG基材的燃点，仿制LIG基材在激光下燃烧。另外还可以使得LIG基材在激光扫描的过程中可以不需要保护气，降低成本和设备复杂程度。同时可以增加激光功率、提高扫描速率，增加生产效率。添加阻燃剂后，生物质LIG的面电阻由2000Ω/square降至80Ω/square。
(5)激光诱导扫描，使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为激光诱导石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是30W，照射功率可以是10％、20％、30％、40％、50％、60％、70％、80％、90％、100％。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域，LIG基材中包含纤维素成分。
实施例28
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.木质素提纯，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-10次过筛处理，筛子需由大到小，依次处理。
(3)水洗与烘干，对木质素进行水洗和烘干处理。
S002.纤维素增强的木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为40-90℃，优选的压力为5-12MPa。
S003.激光诱导扫描，使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为激光诱导石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。激光诱导扫描过程中，LIG基材处于保护气的环境中，保护气可以是还原性和惰性气体，如H2、Ar、N2、SF6或几种气体的混合气体。
使用还原性或惰性气体作为保护气，可有效增强石墨烯功能层表面的疏水性，并可以代替生物质LIG基材的阻燃处理步骤；在SF6氛围下扫描，可将氟元素沉积在石墨烯功能层中，对石墨烯功能层实现改性。
实施例29
本发明的一个实施例提供了一种层状石墨烯复合材料卷对卷生产方法，该方法包括：
通过第一辊单元将纤维素层状材料浸润木质素溶液，得到木质素与纤维素LIG基材。
通过第二辊单元对木质素与纤维素LIG基材进行热压成型。
通过第一激光器对热压成型的木质素与纤维素LIG基材进行激光诱导扫描，在LIG基材表面生成石墨烯功能层。
通过第三辊单元将表面具有石墨烯复合材料浸入改性/催化/掺杂溶液。
通过第二激光器对改性后的石墨烯复合材料再次进行激光扫描，得到改性石墨烯复合材料。
发明人提供一种层状石墨烯复合材料卷对卷转印装置，其包括：第一辊单元，其形成LIG基材；以及第二辊单元，其通过将由第一辊单元提供的LIG基材进行热压成型；以及第一激光器，其将第二辊单元提供的LIG基材表面转化为激光诱导石墨烯，形成石墨烯层状复合材料；以及第三辊单元，其将改性/催化/掺杂溶液浸润至石墨烯层状复合材料中；以及第二激光器，其对浸润了改性/催化/掺杂溶液的石墨烯层状复合材料再进行照射。
本实施例提供的卷对卷(Roll-to-roll processing)石墨烯层状材料生产方法，流程如图8所示，解决了激光单次不连续的照射导致的激光诱导石墨烯生产效率低的问题，实现在含生物质LIG基材上大量制备石墨烯复合材料，卷对卷石墨烯层状材料生产方法具有生产速度快、设备便宜、基板成本低、产量高等优点。
实施例30
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.木质素提纯与改性，包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
(5)木质素改性，对木质素的改性包括进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酞化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚等多种化学反应，增强木质素的耐温和成炭性能。
进一步的，木质素改性步骤中，将木质素进行接枝和酯化，通过化学催化的方法将环氧基团接枝至木质素的酚羟基上，随后与丙烯酸产生酯化反应制备环氧木质素丙烯酸酯溶液，以提高木质素的粘性和高温下的流延性。
S002.纤维素增强的改性木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。改性木质素/纤维素添加量，改性木质素添加量：0-34wt％，优选的改性木质素添加量21wt％。优选的纤维素直径是＞1000nm。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
(4)催化剂改性，在木质素纤维素LIG基材表面加注催化剂，所述催化剂为金属、金属合金、金属/金属氧化物混合物等的乙醇溶液。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。
本实施例所选用的激光器最大激光功率为10W，探头最大移动速度可达80mm/s。所加工器件性能最优状态的参数组合中功率设置为10％，探头移动速度设置为20-50mm/s。
实施例31
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，具体的步骤包括：
S001.木质素提纯，其方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸或者无机酸等。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)有机溶剂萃取和分级，采用丙酮、丁醇、乙醇等有机溶剂萃取和分级木质素，控制木质素的分子质量和粒径大小，去除非功能性成分，提高活性基团的相对含量，增强木质素的可加工性。
(4)水洗与烘干，对木质素进行水洗和烘干处理。
S002.其他元素掺杂的LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将纤维素或纳米纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-60wt％，优选的木质素添加量为10-40wt％。改性木质素/纤维素添加量，改性木质素添加量：0-34wt％，优选的改性木质素添加量50wt％。优选的纤维素直径是＞1500nm。
(2)木质纤维素混合液中添加掺杂剂，如聚(3,4-乙烯二氧噻吩)(PEDOT)、金元素、铁元素、镍元素和金属盐。
(3)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(4)热压成型，木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，使木质素纤维素LIG基材中的前驱体转变为石墨烯。激光的波长可以是9.3-10.6μm、625-740nm、450-480nm、1053nm。激光器包括CO2激光器、红光激光器、蓝光激光器、飞秒激光激光器等。激光器的功率范围是0-50W。LIG基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。可以利用单次或多次照射LIG基材的相同区域。LIG基材中包含纤维素成分。
本实施例所选用的激光器最大激光功率为20W，探头最大移动速度可达80mm/s。所加工器件性能最优状态的参数组合中功率设置为10-30％，探头移动速度设置为10-30mm/s。进行掺杂可以进一步提高LIG产品的性能，如LIG的面电阻、IG/ID参数等。
实施例32
本实施例提供一种石墨烯超级电容器，该石墨烯超级电容器包括封装容器和封装于封装容器内的芯子，以及部分地插入封装容器并与芯子内的石墨烯功能层相连的集流体。其中，该芯子是由隔膜、电解液和石墨烯复合材料卷绕而成的卷状结构。所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与电解液相邻的表面上。
进一步的，隔膜和电解液的结构可以为层叠的吸液式隔膜，所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与吸液式隔膜相邻的表面上。该吸液式隔膜内吸附有电解液。
本实施例所述的石墨烯超级电容器中所述的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转 变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本实施例所述的石墨烯超级电容器的芯子是由两层所述石墨烯复合材料及层叠设于两层所述石墨烯复合材料中间的所述吸液式隔膜卷绕而成的卷状结构，所述集流体包括与一个所述柔性石墨烯复合材料的石墨烯功能层相连的正集流体和与另一个所述石墨烯复合材料的石墨烯功能层相连的负集流体。所述集流体通过导电胶粘接在所述石墨烯功能层上。所述封装容器包括一端封闭而另一端敞开的筒体和用于封堵所述筒体的敞开端的密封塞，其中所述集流体密封地贯穿所述密封塞。超级电容器的结构示意图如图18、图22、图23所示。
所述超级电容器表现出良好的能量-功率性能。部分性能参数如下。以LBEA-A-1-2为例，该编号代表不同物质含量的木质素基环氧丙烯酸酯(LBEA)，所述LEBA为制作石墨烯复合材料的前驱体物质，其中A代表所使用的有机溶剂可溶木质素为丙酮可溶木质素(另B表示丁醇可溶木质素，E表示乙醇可溶木质素)，1代表将有机溶剂可溶木质素以1g的添加量溶于100mL的二甲基亚砜(DMSO)溶液中，2代表每1g木质素中添加2克环氧氯丙烷(ECH)：
表10使用源自不同LBEA前驱体的LIG电极制造的超级电容器参数对比
表11不同木质素种类下的超级电容器参数对比
实施例33
本实施例提供一种石墨烯超级电容器及其使用的石墨烯复合材料的制备方法，该石墨烯超级电容器包括封装容器和封装于封装容器内的芯子，以及部分地插入封装容器并与芯子内的石墨烯功能层相连的集流体。其中，该芯子是由隔膜、电解液和石墨烯复合材料卷绕而成的卷状结构。所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与电解液相邻的表面上。
进一步的，隔膜和电解液的结构可以为层叠的吸液式隔膜，所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与吸液式隔膜相邻的表面上。该吸液式隔膜内吸附有电解液。
本实施例所述的石墨烯超级电容器中所述的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本实施例所述的石墨烯超级电容器的芯子是由两层所述石墨烯复合材料及层叠设于两层所述石墨烯复合材料中间的所述吸液式隔膜卷绕而成的卷状结构，所述集流体包括与一个所述柔性石墨烯复合材料的石墨烯功能层相连的正集流体和与另一个所述石墨烯复合材料的石墨烯功能层相连的负集流体。所述集流体通过导电胶粘接在所述石墨烯功能层上。所述封装容器包括一端封闭而另一端敞开的筒体和用于封堵所述筒体的敞开端的密封塞，其中所述集流体密封地贯穿所述密封塞。超级电容器的结构示意图如图18、图22、图23所示。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基 材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
实施例34
本实施例提供一种石墨烯超级电容器，该石墨烯超级电容器包括封装容器和封装于封装容器内的芯子，以及部分地插入封装容器并与芯子内的石墨烯功能层相连的集流体。其中，该芯子是由隔膜、电解液和石墨烯复合材料卷绕而成的卷状结构。所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与电解液相邻的表面上。
进一步的，隔膜和电解液的结构可以为层叠的吸液式隔膜，所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与吸液式隔膜相邻的表面上。该吸液式隔膜内吸附有电解液。
本实施例所述的石墨烯超级电容器中所述的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本实施例所述的石墨烯超级电容器的石墨烯复合材料的数量为一个，所述石墨烯功能层包括石墨烯正电极功能层和石墨烯负电极功能层，所述石墨烯正电极功能层和石墨烯负电极功能层设于所述基材层上且互不接触，所述集流体包括与石墨烯正电极功能层和石墨烯负电极功能层分别相连的正集流体和负集流体。
所述集流体通过导电胶粘接在所述石墨烯功能层上。所述封装容器包括一端封闭而另一端敞开的筒体和用于封堵所述筒体的敞开端的密封塞，其中所述集流体密封地贯穿所述密封塞。超级电容器的结构示意图如图18、图22、图24所示。
实施例35
本实施例提供一种石墨烯超级电容器及其使用的石墨烯复合材料的制备方法，该石墨烯超级电容器包括封装容器和封装于封装容器内的芯子，以及部分地插入封装容器并与芯子内的石墨烯功能层相连的集流体。其中，该芯子是由隔膜、电解液和石墨烯复合材料卷绕而成的卷状结构。所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与电解液相邻的表面上。
进一步的，隔膜和电解液的结构可以为层叠的吸液式隔膜，所述的石墨烯超级电容器中的石墨烯功能层设于基材层的与吸液式隔膜相邻的表面上。该吸液式隔膜内吸附有电解液。
本实施例所述的石墨烯超级电容器中所述的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转 变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本实施例所述的石墨烯超级电容器的石墨烯复合材料的数量为一个，所述石墨烯功能层包括石墨烯正电极功能层和石墨烯负电极功能层，所述石墨烯正电极功能层和石墨烯负电极功能层设于所述基材层上且互不接触，所述集流体包括与石墨烯正电极功能层和石墨烯负电极功能层分别相连的正集流体和负集流体。
所述集流体通过导电胶粘接在所述石墨烯功能层上。所述封装容器包括一端封闭而另一端敞开的筒体和用于封堵所述筒体的敞开端的密封塞，其中所述集流体密封地贯穿所述密封塞。超级电容器的结构示意图如图18、图22、图24所示。
本发明的一个实施例提供了一种上述石墨烯复合材料的卷对卷生产方法，可进行上述石墨烯复合材料的连续制备，进而实现超级电容器的规模化生产，具体的实施方法包括：
通过第一辊单元将纤维素层状材料浸润木质素溶液，得到木质素与纤维素LIG基材。
通过第二辊单元对木质素与纤维素LIG基材进行热压成型。
通过第一激光器对热压成型的木质素与纤维素LIG基材进行激光诱导扫描，在LIG基材表面生成石墨烯功能层。
进一步的，可以通过第三辊单元将表面具有石墨烯复合材料浸入改性/催化/掺杂溶液。通过第二激光器对改性后的石墨烯复合材料再次进行激光扫描，得到改性石墨烯复合材料。
发明人提供一种层状石墨烯复合材料卷对卷转印装置，其包括：第一辊单元，其形成LIG基材；以及第二辊单元，其通过将由第一辊单元提供的LIG基材进行热压成型；以及第一激光器，其将第二辊单元提供的LIG基材表面转化为激光诱导石墨烯，形成石墨烯层状复合材料；以及第三辊单元，其将改性/催化/掺杂溶液浸润至石墨烯层状复合材料中；以及第二激光器，其对浸润了改性/催化/掺杂溶液的石墨烯层状复合材料再进行照射。
本实施例提供的卷对卷(Roll-to-roll processing)石墨烯层状材料生产方法，流程如图8所示，解决了激光单次不连续的照射导致的激光诱导石墨烯生产效率低的问题，实现在含生物质LIG基材上大量制备石墨烯复合材料，卷对卷石墨烯层状材料生产方法具有生产速度快、设备便宜、基板成本低、产量高等优点。
实施例36
本实施例提供一种石墨烯超级电容器，包括电容器本体，所述电容器本体包括多个单体电容及内极耳。其中，所述多个单体电容中相邻单体电容之间通过内极耳串联连接，所述单体电容包括由石墨烯复核材料构成的石墨烯正极以及石墨烯负极和电解液，所述单体电容的石墨烯正极和第一相邻单体电容的石墨烯负极通过内极耳一体连接，所述单体电容的石墨烯负极和第二相邻单体电容的石墨烯正极通过内极耳一体连 接；所述石墨烯正极和石墨烯负极呈现叉指状、平行条状、螺旋状或其组合形状中的任一种。所述外包装用于对所述电容器本体进行封装。本实施例超级电容器的示意图如图25、图26所示。所述极耳与集流体的功能均主要为将器件内部产生的电流汇集起来以便形成较大的电流对外输出。
本实施例所述的石墨烯超级电容器中所述的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
进一步的，激光可以为CO2激光光源，当激光为CO2激光时，其LIG前驱体可以为PI、GO film、PI-LSG+Ni-CATMOF、PI-LSG+PANI、PI-LSG+MnO2、PI-LSG+FeOOH/LSG+MnO2、PI-LSG+Fe3O4/LSG、Hydrated GO film、H3BO3/PI中的一种。其电解液可以为Hydrated GO、H2SO4、BMIM-BF4、PVA/H2SO4、BMIM、PVA/LiCl中的一种，相应的超级电容器的电压范围为0.3-250V，CA为0-1000mF·cm-2，Cv为0-150F·cm-3，Ev为0-110mWh·cm-3，Pv为0-100W·cm-3。
优选的，激光为200-1200nm激光时，其LIG前驱体可以为GO/HAuCl4、GO/Ni、GO film、PI、GO film、PI-LSG+Ni-CATMOF、PI-LSG+PANI、PI-LSG+MnO2、PI-LSG+FeOOH/LSG+MnO2、PI-LSG+Fe3O4/LSG、Hydrated GO film、H3BO3/PI中的一种。其电解液可以为FS-IL、Hydrated GO、H2SO4、BMIM-BF4、PVA/H2SO4、BMIM、PVA/LiCl中的一种，相应的超级电容器的电压范围为0.3-250V，CA为0-1000mF·cm-2，Cv为0-150F·cm-3，Ev为0-110mWh·cm-3，Pv为0-2500W·cm-3。
实施例37
本实施例提供一种石墨烯超级电容器，包括电容器本体，所述电容器本体包括多个单体电容及内极耳。其中，所述多个单体电容中相邻单体电容之间通过内极耳串联连接，所述单体电容包括由石墨烯复核材料构成的石墨烯正极以及石墨烯负极和电解液，所述单体电容的石墨烯正极和第一相邻单体电容的石墨烯负极通过内极耳一体连接，所述单体电容的石墨烯负极和第二相邻单体电容的石墨烯正极通过内极耳一体连接；所述石墨烯正极和石墨烯负极呈现叉指状、平行条状、螺旋状或其组合形状中的任一种。所述外包装用于对所述电容器本体进行封装。本实施例超级电容器的示意图如图25、图26所示。
本实施例所述的石墨烯超级电容器中所述的石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
实施例38
本实施例提供了一种石墨烯应变传感器，用于提高石墨烯应变传感器的应用范围及应用场景。所述石墨烯应变传感器包括由石墨烯复合材料构成的导电层。应变传感器的相关示意图如图19、图27、图28所示。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
所述导电层包括由基材层和石墨烯功能层形成的堆叠结构。具体地，石墨烯应变传感器中的导电层可以包括由基材层和多层石墨烯功能层堆叠形成的堆叠结构，例如，可以由基材层和双层石墨烯功能层堆叠组成，也可以由三层石墨烯功能层堆叠组成。导电层中的多层石墨烯功能层之间相堆叠，但各石墨烯功能层之间的作用力弱于单层石墨烯功能层自身层之间的作用力，因而，在形变的情况下，同一导电层中的各石墨烯功能层之间可能会发生滑移，但同一多层石墨烯功能层中的各层石墨烯仍相互搭接。所述石墨烯应变传感器，还包括连接电极，所述连接电极包括第一电极及第二电极；所述第一电极及第二电极分别设置在所述导电层的相对两端。
所述应变传感器的部分性能参数为：向下弯折(拉伸)时，当弯折程度在环境条件下从0增加到10mm(灵敏度为3.29Ω/mm)时，传感器电阻(LIG在凸侧)从43增加到76Ω；向上弯折(压缩)时，电阻(LIG在凹侧)则从43Ω下降到19Ω(灵敏度为2.55Ω/mm)。
进一步的可以发现，可穿戴传感器的性能受LBEA中环氧丙烯酸酯含量的影响，该含量越高，复合纸的柔韧性越强，显着提高了传感器的灵敏度和测量范围。LBEA-A-10-1和LBEA-A-10-0.5衍生的LIG传感器的拉伸灵敏度分别为3.10和1.96Ω/mm，压缩灵敏度分别为2.20和2.02Ω/mm，测量范围分别为±8和±5mm。
表12不同木质素种类下的应变传感器参数对比
实施例39
本实施例提供了一种石墨烯应变传感器，用于提高石墨烯应变传感器的应用范围及应用场景。所述石墨烯应变传感器包括由石墨烯复合材料构成的导电层。应变传感器的相关示意图如图19、图27、图28所示。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
所述导电层包括由基材层和石墨烯功能层形成的堆叠结构。具体地，石墨烯应变传感器中的导电层可以包括由基材层和多层石墨烯功能层堆叠形成的堆叠结构，例如，可以由基材层和双层石墨烯功能层堆叠组成，也可以由三层石墨烯功能层堆叠组成。导电层中的多层石墨烯功能层之间相堆叠，但各石墨烯功能层之间的作用力弱于单层石墨烯功能层自身层之间的作用力，因而，在形变的情况下，同一导电层中的各石墨烯功能层之间可能会发生滑移，但同一多层石墨烯功能层中的各层石墨烯仍相互搭接。所述石墨烯应变传感器，还包括连接电极，所述连接电极包括第一电极及第二电极；所述第一电极及第二电极分别设置在所述导电层的相对两端。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
所述应变传感器的部分性能参数为：向下弯折(拉伸)时，当弯折程度在环境条件下从0增加到10mm(灵敏度为3.29Ω/mm)时，传感器电阻(LIG在凸侧)从43增加到76Ω；向上弯折(压缩)时，电阻(LIG在凹侧)则从43Ω下降到19Ω(灵敏度为2.55Ω/mm)。
进一步的可以发现，可穿戴传感器的性能受LBEA中环氧丙烯酸酯含量的影响，该含量越高，复合纸的柔韧性越强，显着提高了传感器的灵敏度和测量范围。LBEA-A-10-1和LBEA-A-10-0.5衍生的LIG传感器的拉伸灵敏度分别为3.10和1.96Ω/mm，压缩灵敏度分别为2.20和2.02Ω/mm，测量范围分别为±8和±5mm。
实施例40
本实施例提供了一种石墨烯应变传感器，所述石墨烯应变传感器包括：含有基材层和石墨烯功能层的石墨烯复合材料；基材层和石墨烯功能层分别连接的电极；所述电极与基材层之间形成有塑化层。进一步的，石墨烯复合材料为柔性石墨烯复合材料。应变传感器的相关示意图如图19、图27、图28所示。
所述柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
所述石墨烯应变传感器的塑化层为具有粘结剂的柔性胶带或无粘结剂的薄膜。所述塑化层在器件应变时能够降低所述塑化层所覆盖区域的形变，保护其上的电极，使其电阻不发生变化。所述电极为导电材料，所述电极用于连接石墨烯功能层，以及连接引出导线。
该具体实施方式中，所述电极和石墨烯功能层边界上覆盖有应力缓冲层，用于释放电极和石墨烯功能层边界的应力，增强器件应变时电极和石墨烯功能层之间的电学连接。
所述应变传感器的部分性能参数为：向下弯折(拉伸)时，当弯折程度在环境条件下从0增加到10mm(灵敏度为3.29Ω/mm)时，传感器电阻(LIG在凸侧)从43增加到76Ω；向上弯折(压缩)时，电阻(LIG在凹侧)则从43Ω下降到19Ω(灵敏度为2.55Ω/mm)。
进一步的可以发现，可穿戴传感器的性能受LBEA中环氧丙烯酸酯含量的影响，该含量越高，复合纸的柔韧性越强，显着提高了传感器的灵敏度和测量范围。LBEA-A-10-1和LBEA-A-10-0.5衍生的LIG传感器的拉伸灵敏度分别为3.10和1.96Ω/mm，压缩灵敏度分别为2.20和2.02Ω/mm，测量范围分别为±8和±5mm。
实施例41
本实施例提供了一种石墨烯应变传感器，所述石墨烯应变传感器包括：含有基材层和石墨烯功能层的石墨烯复合材料；基材层和石墨烯功能层分别连接的电极；所述电极与基材层之间形成有塑化层。进一步的，石墨烯复合材料为柔性石墨烯复合材料。应变传感器的相关示意图如图19、图27、图28所示。
所述柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
所述石墨烯应变传感器的塑化层为具有粘结剂的柔性胶带或无粘结剂的薄膜。所述塑化层在器件应变时能够降低所述塑化层所覆盖区域的形变，保护其上的电极，使其电阻不发生变化。所述电极为导电材料，所述电极用于连接石墨烯功能层，以及连接引出导线。
该具体实施方式中，所述电极和石墨烯功能层边界上覆盖有应力缓冲层，用于释放电极和石墨烯功能层边界的应力，增强器件应变时电极和石墨烯功能层之间的电学连接。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和 皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
所述应变传感器的部分性能参数为：向下弯折(拉伸)时，当弯折程度在环境条件下从0增加到10mm(灵敏度为3.29Ω/mm)时，传感器电阻(LIG在凸侧)从43增加到76Ω；向上弯折(压缩)时，电阻(LIG在凹侧)则从43Ω下降到19Ω(灵敏度为2.55Ω/mm)。
进一步的可以发现，可穿戴传感器的性能受LBEA中环氧丙烯酸酯含量的影响，该含量越高，复合纸的柔韧性越强，显着提高了传感器的灵敏度和测量范围。LBEA-A-10-1和LBEA-A-10-0.5衍生的LIG传感器的拉伸灵敏度分别为3.10和1.96Ω/mm，压缩灵敏度分别为2.20和2.02Ω/mm，测量范分别为±8和±5mm。
实施例42
本实施例提供了一种石墨烯焦耳加热器，包括石墨烯复合材料，所述石墨烯复合材料的两端分别粘贴有电极，所述电极与石墨烯复合材料的接缝处涂覆有导电银漆。所述石墨烯焦耳加热器可以为石墨烯复合材料所覆盖的加热区进行加热，所述加热的方式包括将石墨烯焦耳加热器贴附在物体表面或嵌入物体内部进行加热；具体的是将电源的正极和负极分别与石墨烯焦耳加热器的两个电极相连，输入电功率，所述激光诱导石墨烯纸加热器将电能转换成焦耳热对物体进行加热。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
所述焦耳加热器拥有出色的加热性能，其部分性能参数为：最大加热速率约为3.21℃/s。当输入电流功率从0.05增加到2.0W时，LIG的稳态温度相应地从28.7增加到125℃。随着电压强度从1增加到5V/cm2，源自LBEA-A-10-2、LBEA-E-10-2和LBEA-B-10-2的LIG加热器的平衡温度分别从29.7、28.7和29.0℃至131.2、125.1和91.3℃。
实施例43
本实施例提供了一种石墨烯焦耳加热器，包括石墨烯复合材料，所述石墨烯复合材料的两端分别粘贴有电极，所述电极与石墨烯复合材料的接缝处涂覆有导电银漆。所述石墨烯焦耳加热器可以为石墨烯复合材料所覆盖的加热区进行加热，所述加热的方式包括将石墨烯焦耳加热器贴附在物体表面或嵌入物体内部进行加热；具体的是将电源的正极和负极分别与石墨烯焦耳加热器的两个电极相连，输入电功率，所述激光诱导石墨烯纸加热器将电能转换成焦耳热对物体进行加热。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
所述焦耳加热器拥有出色的加热性能，其部分性能参数为：最大加热速率约为3.21℃/s。当输入电流功率从0.05增加到2.0W时，LIG的稳态温度相应地从28.7增加到125℃。随着电压强度从1增加到5V/cm2，源自LBEA-A-10-2、LBEA-E-10-2和LBEA-B-10-2的LIG加热器的平衡温度分别从29.7、28.7和29.0℃至131.2、125.1和91.3℃。
实施例44
本实施例提供一种基于石墨烯复合材料的多巴胺传感器。所述多巴胺传感器包括所述石墨烯复合材料的两端分别粘贴有电极，所述电极与石墨烯复合材料的接缝处涂覆有导电银漆。所述电极表面修饰有石墨烯复合材料，然后在修饰好的电极上滴加莱克多巴胺抗原，得到检测莱克多巴胺的电化学免疫传感器。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
实施例45
本实施例提供一种基于石墨烯复合材料的多巴胺传感器。所述多巴胺传感器包括所述石墨烯复合材料的两端分别粘贴有电极，所述电极与石墨烯复合材料的接缝处涂覆有导电银漆。所述电极表面修饰有石墨烯复合材料，然后在修饰好的电极上滴加莱克多巴胺抗原，得到检测莱克多巴胺的电化学免疫传感器。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
实施例46
本实施例提供一种基于石墨烯复合材料的气体传感器。所述石墨烯气体传感器包括石墨烯复合材料，所述石墨烯复合材料包括基材层和石墨烯功能层，所述石墨烯功能层用作石墨烯电极；所述石墨烯气体传感器对自身所处环境中的待测气体进行检测，输出用于表征待测气体浓度的电信号，包括：当所述石墨烯气体传感器置于气体环境时，所述石墨烯电极材料表面吸附气体分子后引起电阻率变化，进而输出用于表征气体浓度的电信号。之后，再由微处理器基于气体浓度值与电信号值之间的对应关系，将所输出的用于表征待测气体浓度的电信号对应的电信号值换算为待测气体浓度值。实施例中气体传感器的相关示意图如图29、图30所示。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
所述气体传感器的部分参数性能为：所述石墨烯电极对H2的灵敏度最高，其次是CO2、压缩空气和N2。平均响应和恢复时间分别约为12和18秒。
实施例47
本实施例提供一种基于石墨烯复合材料的气体传感器。所述石墨烯气体传感器包括石墨烯复合材料，所述石墨烯复合材料包括基材层和石墨烯功能层，所述石墨烯功能层用作石墨烯电极；所述石墨烯气体传感器对自身所处环境中的待测气体进行检测，输出用于表征待测气体浓度的电信号，包括：当所述石墨烯气体传感器置于气体环境时，所述石墨烯电极材料表面吸附气体分子后引起电阻率变化，进而输出用于表征气体浓度的电信号。之后，再由微处理器基于气体浓度值与电信号值之间的对应关系，将所输出的用于表征待测气体浓度的电信号对应的电信号值换算为待测气体浓度值。实施例中气体传感器的相关示意图如图29、图30所示。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
本发明的一个实施例提供了一种上述石墨烯复合材料的制备方法，该方法用激光照射纤维素复合的含前驱体LIG基材，制备石墨烯复合材料。具体的实施方法包括：
(1)制备纤维素复合的包含前驱体的LIG基材。前驱体的添加比例可以是2-45wt％，优选的添加比例可以是15-25wt％。前驱体可以是氧化石墨烯、聚酰亚胺、木质素。
(2)设置激光加工参数对进行激光照射。激光的波长可以是9.3-10.6μm、625-740nm、505-566nm、450-480nm、10-450nm、1053nm。激光器包括CO2激光器、红光激光器、绿光激光器、蓝光激光器、飞秒和皮秒激光激光器等。LIG基材表面承受的激光强度需要大于3J/cm2，小于40J/cm2，优选的激光强度是5.5-20J/cm2。可以利用上述参数的激光单次或多次照射LIG基材的相同区域，不同激光强度TEM结果如图14所示。
本发明的一个实施例中，激光照射至LIG基材表面的时候可聚焦也可失焦扫描(-3.0-3.0mm)，失焦扫描时，激光点为圆形，在激光头平移过程中每组圆形会有重叠，重叠区相当于扫描了两次及以上。
本发明的一个实施例中，前驱体粒径是10nm-500nm，纤维素直径＞1000nm。
本发明的一个实施例中，前驱体的添加量大于10wt％有利于对纤维素纤维的包裹，保护纤维素在激光扫描过程中不被碳化，维持纤维素的束管结构稳定性，从而使得最终生成的石墨烯功能层更好的附着于基材层表面。前驱体添加量过低会导致纤维素表面覆盖的前驱体过薄，无法有效保护纤维素免受激光照射。而前驱体添加量过高会影响石墨烯复合材料的柔韧性。LIG基材的厚度是0.02-0.5mm。
所述气体传感器的部分参数性能为：所述石墨烯电极对H2的灵敏度最高，其次是CO2、压缩空气和N2。平均响应和恢复时间分别约为12和18秒。
实施例48
本实施例提供了一种用于电芬顿净水的电极及电极的生产方法，所述电极基于本发明所提供的石墨烯复合材料，提出了一种直接合成可再生LIG电极的直接CO2激光刻划木质纤维素为基础的牛皮纸。具体包括如下步骤：
可直接合成可再生LIG电极的直接CO2激光刻划木质纤维素为基础的牛皮纸制备。
将磁性FeNi3纳米粒子被夹在两个LIG之间作为芬顿催化剂，得到FeNi3的LIG电极
在交联溶液中用聚乙烯醇(PVA)对FeNi3的LIG电极进行包覆
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
实施例49
本实施例提供了一种用于电芬顿净水的电极及电极的生产方法，所述电极基于本发明所提供的石墨烯复合材料，提出了一种直接合成可再生LIG电极的直接CO2激光刻划木质纤维素为基础的牛皮纸。具体包括如下步骤，流程如图31所示：
通过第一辊单元将纤维素层状材料浸润木质素溶液，得到木质素与纤维素LIG基材。
通过第二辊单元对木质素与纤维素LIG基材进行热压成型。
通过第一激光器对热压成型的木质素与纤维素LIG基材进行激光诱导扫描，在LIG基材表面生成石墨烯功能层。
通过第三辊单元将表面具有石墨烯复合材料浸入FeNi3溶液。
通过第二激光器对改性后的石墨烯复合材料再次进行激光扫描，得到FeNi3的LIG电极。
所述石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面，如图9和10所示。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层的部分转变为了碳化纤维素；部分纤维素与碳化纤维素的分子互相缠结形成网状结构，激光诱导石墨烯嵌套于该网状结构中，嵌套结构如图17所示。
实施例50
本实施例提供了一种石墨烯转印工艺，具体的步骤包括：
(1)木质素溶液配制。将一定量的木质素均匀溶解于氢氧化钠(NaOH)溶液。
(2)木质素/PVA交联体系建立。按比例向木质素溶液中添加聚乙烯醇(PVA)，高温溶解且搅拌混匀后，加入一定量的交联剂和增塑剂。
(3)流延法铺膜。将木质素/PVA溶液倒入模具中，在恒温恒湿条件下固化成型。
(4)激光直写扫描。调节激光参数，在木质素/PVA膜表面直接激光扫描，制备LIG。
(5)硅胶溶解法转印。用匀胶机在LIG表面均匀浇筑硅胶溶液，加热固化后，转入水中，木质素/PVA遇水溶解，LIG转印至柔性可弯曲的硅胶上。
实施例51
本实施例提供了一种石墨烯转印工艺，具体的步骤包括：
(1)木质素溶液配制。将聚乙烯醇(PVA)溶解在去离子水中，在90℃下连续搅拌40分钟，PVA：去离子水＝1：10。然后，将0.5g、1g和1.5g牛皮纸木质素溶解在10g2％中分别为NaOH溶液。然后将10g PVA液体倒入每种溶解的木质素溶液中并搅拌直至获得均匀的混合物。然后，将深棕色混合物转移到塑料盘上，然后放入温度为35℃，湿度为15％～50％的培养箱中。之后干燥取出。
(2)木质素/PVA交联体系建立。按比例向木质素溶液中添加聚乙烯醇(PVA)，高温溶解且搅拌混匀后，加入一定量的交联剂和增塑剂。将龙皮预聚物混合物(A部分/B部分＝1:1，w/w)倒在LIG样品上。这里使用旋涂机(型号WS-650MZ-23NPPB)，旋转速度为3000转/分钟。然后，将样品放入烘箱中35℃固化30分钟。固化后，将整个样品放入去离子水中，以帮助LIG从木质素前体上脱落。然后将得到的龙皮LIG再次放入35℃烘箱中烘干20分钟。
(3)流延法铺膜。将木质素/PVA溶液倒入模具中，在恒温恒湿条件下固化成型。
(4)激光直写扫描。调节激光参数，在木质素/PVA膜表面直接激光扫描，制备LIG。在环境条件下使用30W、10.6μmCO2激光切割机(Universal Laser Systems VLS3.50激光切割机/雕刻机)形成LIG。 对于所有激光工艺，每英寸1000个脉冲(PPI)、10％的速度和额外的2毫米Z轴距离都是固定的。不同的激光功率20％、30％、40％依次施加在每个前驱体上。激光扫描的区域是一个长30mm、宽5mm的长方形。
(5)硅胶溶解法转印。用匀胶机在LIG表面均匀浇筑硅胶溶液，加热固化后，转入水中，木质素/PVA遇水溶解，LIG转印至柔性可弯曲的硅胶上。
实施例52
本发明的一个实施例提供了一种柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。石墨烯功能层含有激光诱导石墨烯，具有三维孔道结构。在石墨烯层状复合材料的结构中，部分纤维素连接了基材层与石墨烯功能层，其进入石墨烯功能层部分转变为了碳化纤维素；部分纤维素(含碳化纤维素)分子互相缠结形成网状结构，部分激光诱导石墨烯嵌套于该网状结构中。
本发明的一个实施例中，石墨烯功能层中的石墨烯与激光诱导石墨烯的比例是1:1-1:2，石墨烯与激光诱导石墨烯比例的检测方法是TEM检测。拉曼光谱中，IG/ID为1.0-3.3，I2D/IG为0.4-0.8，La为20-45mm。石墨烯功能层的面电阻为18-150Ω/square。石墨烯功能层的导电率为50-200S/cm。石墨烯功能层的比表面积为10-350m2/g。石墨烯功能层的孔径为0-750nm。石墨烯功能层的厚度为0.05-35μm。石墨烯功能层的C相对含量为85wt％-93wt％、O相对含量为5wt％-10wt％、N相对含量为2wt％-5wt％，如图3至图7所示。使用的激光光源为蓝光光源。
本发明的一个实施例中，基材层可以是含有叶酸的纤维素。制备中使用叶酸对纤维素进行改性，纤维素在基材层中形成相互交错的网状结构，叶酸改性的纤维纸基材层的透气率为1700-2200mL·mm·(cm2·h·mmAq)-1。聚酰亚胺纤维纸的抗张指数：＞40N·m/g，撕裂指数：＞30mM·m2/g，电常数：1.5-2.0，介质损耗因数：3.1×10-3-6.5×10-3。面电阻范围是90-300Ω/square。
实施例53
本发明的一个实施例提供了一种优选的生物基的柔性石墨烯复合材料，包括基材层、石墨烯功能层，石墨烯功能层附着于基材层表面。基材层包括叶酸改性的纤维素和纳米木质素。纳米木质素可以显著的提高激光诱导石墨烯品质，同时纳米木质素的粒径越小，激光诱导石墨烯的品质越好,。
表13含有纤维素及不同纳米木质素粒径基材层参数
纳米木质素可以更好的包裹于纤维素表面，保护纳米纤维素在激光照射过程中不被分解。同时纳米木质素转变为激光诱导石墨烯。从而提高石墨烯功能层品质。
实施例54
本发明的一个实施例提供了一种石墨烯复合材料的制备方法，该方法通过激光将含有纤维素的LIG基材转化石墨烯。具体的步骤包括：
S001.木质素提纯，木质素提纯的方法包括如下步骤，
(1)酸洗，对木质素进行酸洗，使用的酸包括盐酸、硫酸等无机酸。
(2)过筛，对木质素进行1-5次过筛处理，筛子需由大到小，依次处理。
(3)水洗与烘干，对木质素进行水洗和烘干处理。
S002.纤维素增强的含木质素LIG基材制备，其方法包括如下步骤，
(1)木质素与纤维素混合液制备，将叶酸、纤维素加入木质素溶液中，搅拌、超声、乳化后制成木质纤维素混合溶液。木质素添加量是0-41wt％，优选的木质素添加量为29wt％。优选的纤维素直径是＞1000nm，叶酸的添加量为5-25wt％。
(2)铺膜，通过流延法或真空抽滤法将木质素与纤维素混合液制备成木质素纤维素湿膜。
(3)热压成型，将木质素纤维素湿膜在40-150℃、1-15MPa下固化成膜，成为木质素纤维素LIG基材，优选的温度为50-100℃，优选的压力为5-10MPa。
S003.激光诱导扫描，
使用激光照射木质素纤维素LIG基材，在木质素纤维素LIG基材表面生成石墨烯功能层。激光的波长是400-500nm。激光器使用的是蓝光激光器。激光器的功率范围是0-50W。基材表面承受的激光强度需要＞3J/cm2，优选的激光强度是＞5.5J/cm2。激光器的功率强度可以是65％、70％、75％、80％、85％、90％、100％。可以利用单次或多次照射基材的相同区域。

Claims (13)

  1. 一种激光诱导石墨烯，包含基材层、石墨烯功能层，其特征在于，在所述激光诱导石墨烯的基材层中含有改性前驱体，所述改性前驱体包括生物质类材料、合成类材料、矿物类材料的一种或其组合，所述改性前驱体的粒径为50-500nm；在所述激光诱导石墨烯中含有纤维素，所述石墨烯功能层包括激光石墨烯，所述纤维素分散于基材与石墨烯功能层，处于石墨烯功能层的纤维素全部或部分转化为了碳化纤维素。
  2. 如权利要求1所述的激光诱导石墨烯，其特征在于，所述纤维素包括处于所述基材层与所述石墨烯功能层过渡区域的纤维素，所述纤维素连接了所述基材层与所述石墨烯功能层，所述纤维素包括分子互相缠结形成网状结构的纤维素与碳化纤维素，部分激光石墨烯嵌套于所述网状结构。
  3. 如权利要求2所述的激光诱导石墨烯，其特征在于，前驱体是生物质类材料，生物质类材料的成分包括木质素、单宁酸、多酚、黄酮类化合物的一种或其组合；合成类材料包括光刻胶、聚酰亚胺膜、聚酰亚胺纤维纸、聚酰亚胺泡沫海绵、聚砜类聚合物、特氟龙、酚醛树脂、ABS塑料、聚苯乙烯聚合物的一种或其组合；矿物类材料包括煤炭、炭黑、氧化石墨烯、石墨的一种或其组合。
  4. 如权利要求3所述的激光诱导石墨烯，其特征在于，所述的改性前驱体为改性木质素，所述改性木质素有环氧基团和脂类基团的至少一种。
  5. 如权利要求4所述的激光诱导石墨烯，其特征在于，所述改性木质素是由Kraft木质素、碱木质素、脱碱木质素、木质素硫酸盐的一种或其组合改性制备的产物。
  6. 如权利要求1-5中任意一项所述的激光诱导石墨烯，其特征在于，所述改性前驱体含有阻燃基团，所述阻燃基团是磷酸基团、卤素基团、硅系基团的一种或其组合。
  7. 一种激光诱导石墨烯的制备方法，其特征在于，使用激光照射激光诱导石墨烯基材制备激光诱导石墨烯，所述激光的波长范围是9.3-10.6μm、625-740nm、450-480nm、1053nm，激光诱导石墨烯基材表面承受的激光强度范围是3J/cm2-40J/cm2，所述激光诱导石墨烯基材含有改性前驱体，所述激光诱导石墨烯基材的厚度是0.02-0.5mm。
  8. 如权利要求7所述的制备方法，其特征在于，所述改性前驱体的改性方法包括氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酯化、磺化、烷基化、卤化、硝化、缩聚、接枝、酯化、共聚的一种或其组合。
  9. 如权利要求8所述的制备方法，其特征在于所述改性前驱体的改性方法使得改性前驱体有环氧基团和脂类基团。
  10. 如权利要求9所述的制备方法，其特征在于，所述激光诱导石墨烯基材中还含有纤维素，所述纤维素的直径小于100nm、长径比是1000-1500；或者所述纤维素直径是0.1-120um、长度是0.1-5mm。
  11. 如权利要求10所述的制备方法，其特征在于，所述改性前驱体是改性木质素，所述改性木质素的粒径是10nm-500nm。
  12. 如权利要求11所述的制备方法，其特征在于，所述激光诱导石墨烯基材中的所述改性木质素添加量是0-34wt％。
  13. 如权利要求12所述的制备方法，其特征在于，所述激光诱导石墨烯基材中的所述改性木质素添加量是21wt％。
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