CN109792055A - Metal foil film collector in conjunction with humic acid and the battery and supercapacitor containing it - Google Patents

Metal foil film collector in conjunction with humic acid and the battery and supercapacitor containing it Download PDF

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Publication number
CN109792055A
CN109792055A CN201780060219.2A CN201780060219A CN109792055A CN 109792055 A CN109792055 A CN 109792055A CN 201780060219 A CN201780060219 A CN 201780060219A CN 109792055 A CN109792055 A CN 109792055A
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ha
film
graphene
collector
less
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CN201780060219.2A
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Chinese (zh)
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阿茹娜·扎姆
张博增
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纳米技术仪器公司
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Priority to US15/243,589 priority Critical
Priority to US15/243,589 priority patent/US10014519B2/en
Priority to US15/243,606 priority patent/US20180053931A1/en
Priority to US15/243,606 priority
Application filed by 纳米技术仪器公司 filed Critical 纳米技术仪器公司
Priority to PCT/US2017/018708 priority patent/WO2018038764A1/en
Publication of CN109792055A publication Critical patent/CN109792055A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00Hybrid cells; Manufacture thereof
    • H01M12/08Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/66Current collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/66Current collectors
    • H01G11/68Current collectors characterised by their materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/66Current collectors
    • H01G11/70Current collectors characterised by their structures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/661Metal or alloys, e.g. alloy coatings
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/663Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/665Composites
    • H01M4/667Composites in the form of layers, e.g. coatings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/128Hybrid cells composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Abstract

The metal foil collector of a kind of battery or the combination humic acid in supercapacitor, the collector include: (a) thin metal foil, and there are two opposite but parallel main surfaces for the thin metal foil tool;(b) film of the mixture of humic acid (HA) or HA and graphene, the film have lonsdaleite plane, and wherein HA or both HA and graphene are chemically bonded at least one of described two main surfaces;Wherein the film has thickness from 10nm to 10 μm, by weight from 0.01% to 10% oxygen content, 0.335 to 0.50nm interplanar spacing between lonsdaleite plane, from 1.3 to 2.2g/cm3Phsyical density, all lonsdaleite planar orientations are to be substantially parallel to each other and be parallel to the main surface, when independent measurement in the case where no metal foil, show thermal conductivity greater than 500W/mK, and/or are greater than the conductivity of 1,500S/cm.

Description

Metal foil film collector in conjunction with humic acid and battery and super electricity containing it Container

Cross reference to related applications

This application claims the U.S. Patent Application No.s 15/243589 and 15/243606 that each comfortable August in 2016 is submitted on the 22nd Priority, these patent applications are incorporated herein by quoting mode.

Technical field

The present invention provides a kind of for lithium battery or the collector of supercapacitor.The collector is to be combined with height The metal foil of highly conductive property graphite film derived from the film or humic acid of the humic acid of orientation.

Background technique

Present patent application is related to a kind of collector, and the collector and lithium cell are (for example, lithium-ion electric core, lithium-metal electricity Core or lithium-ion capacitor), supercapacitor, non-lithium battery (such as zinc-air battery core, nickel metal hydride battery, sodium ion Battery core and magnesium ion battery core) and other electrochemical energy storage battery cores anode electrode (anode active material layers) or cathode Electrode (cathode active material) works together.The application is not the one of anode active material layers or cathode active material itself Part.

Lithium-metal battery core includes conventional lithium-metal rechargeable battery core (for example, using lithium foil as anode and making Use MnO2Particle is as active material of cathode), lithium-air battery core (Li- air), lithium-sulphur battery core (Li-S) and emerging lithium- Graphene battery core (Li- graphene, use graphene film as active material of cathode), (Li-CNT makes lithium-carbon nanotube battery core Use CNT as cathode) and lithium-nano-sized carbon battery core (Li-C, use carbon nano-fiber or other nano-carbon materials as yin Pole).Anode and/or cathode active material can contain some lithiums, or can before battery core assembling prelithiation or later Prelithiation immediately.

Rechargable lithium ion (Li ion), lithium metal, lithium-sulphur and Li metal-air battery are considered as electronic The promising electricity of vehicle (EV), hybrid electric vehicle (HEV) and portable electronic device (such as laptop computer and mobile phone) Source.With as active material of positive electrode any other metal or metal-intercalation compound (in addition to Li4.4Si has 4, The specific capacity of 200mAh/g) it compares, the lithium as metallic element has highest lithium storage volume (3,861mAh/g).Therefore, In general, Li metal battery (with lithium anodes) is with being significantly higher than traditional lithium-ion battery (with graphite anode) Energy density.

In history, rechargeable lithium metal battery be using the non-lithiated compounds with relatively high specific capacity such as TiS2、MoS2、MnO2、CoO2And V2O5As active material of cathode production, these active material of cathode and lithium anodes coupling It closes.When the cell is discharged, lithium ion is transferred to cathode from lithium anodes by electrolyte, and cathode becomes lithiumation.It is unfortunate Ground is, in duplicate charging and discharging, lithium metal causes to form dendrite at anode, and the dendrite finally causes internal short Road, thermal runaway and explosion.Due to a series of accidents related with this problem, stopped in early stage nineteen nineties The production of the secondary cell of these types instead lithium ion battery.Even if now, being filled for EV, HEV and microelectronics For setting application, cyclical stability and safety issue, which are still, interferes Li metal battery (such as lithium-sulphur and lithium-transition metal Oxide battery core) further commercialized principal element.

The hair of lithium ion secondary battery is resulted in by the worry promotion of the aforementioned safety to early stage lithium metal secondary cell Exhibition, in a lithium ion secondary battery, carbonaceous material (for example, natural graphite particles) replace pure lithium metal piece or film living as anode Property material.Carbonaceous material absorbs lithium respectively during the recharge phase and discharge regime of lithium ion battery operation and (such as passes through The intercalation of lithium ion or atom between graphene planes) and desorption lithium ion.The carbonaceous material can be mainly comprising can be with With the graphite of lithium intercalation, and gained graphite intercalation compound can be expressed as LixC6, wherein x is typically less than 1 (wherein graphite Specific capacity < 372mAh/g).

It is current although lithium ion (Li ion) battery is the promising energy accumulating device for electro-motive vehicle Cost, safety and performance objective (such as high-energy-density, high-energy density, good has not yet been reached in the Li ion battery of technical level Cyclical stability and long circulation life).Li ion battery core typically uses lithium transition-metal oxide or phosphate as opposite The deintercalation/be embedded in Li again under high potential in carbon negative electrode (anode)+Positive electrode (cathode).Based on lithium transition-metal oxide Or the specific capacity of phosphatic active material of cathode is typically in the range of 140-170mAh/g.Therefore, with graphite anode and Specific energy (weight energy based on the commercially available Li ion battery core that lithium transition-metal oxide or phosphatic cathode are characterized Density) typically 120-220Wh/kg, most typically in the range of 150-200Wh/kg.Corresponding exemplary energy density (volume energy density) range is from 400Wh/L to 550Wh/L.Under the conditions of high charge-discharge magnification, energy density is even lower. If it is two to three times low that these energy values ratios make battery powered electric vehicle be widely accepted required energy values.

Typical battery battery core is made of following item: (a) anode collector (b) is integrated to anode collection with adhesive resin (also referred to as anode active material layers typically comprise active material of positive electrode, conductive filler and adhesive to the anode electrode of fluid Resin Composition), (c) electrolyte/diaphragm, (d) (also referred to as cathode active material typically comprises cathode activity to cathode electrode Material, conductive filler and adhesive resin), it (e) is integrated to the cathode current collector of cathode electrode with adhesive resin, (f) connects To the metal tabs of external cabling (external wiring), and (g) it is wrapped in every other portion in addition to these tabs Shell around part.

Collector (typically aluminium foil (at cathode) and copper foil (at anode)) accounts for lithium ion battery by weight about 15%-20% and 10%-15% is counted at cost.Therefore, thinner and lighter foil will be preferred.However, in the presence of with current techniques The horizontal relevant several main problems of collector: (a) due to being easy corrugation and tearing, thinner foil tends to more expensive and more It is difficult to work with;(b) collector must be that electrochemistry is steady relative to battery core component within the scope of the operation potential window of electrode Fixed.In fact, the internal resistance that mainly the lasting corrosion of the collector as caused by electrolyte may cause battery is gradually increased, this is led Cause continuous loss or the cycle life of apparent capacity poor;(c) oxidation of metal collector is strong exothermal reaction, which may Facilitate the thermal runaway of lithium battery significantly.

Therefore, for the cost of battery, weight, safety and performance, collector is vital.Instead of metal, The solid metal or plastics of graphene or graphene coating have been considered as potential current collector material, as being listed below It is summarized in bibliography:

1.Li Wang、Xiangming He、Jianjun Li、Jian Gao、Mou Fang、Guangyu Tian、 Jianlong Wang, Shoushan Fan, " Graphene-coated plastic film as current collector For lithium/sulfur batteries is [as graphene-coating plastics for lithium/sulphur battery collector Film] ", J.Power Source [power supply magazine], 239 (2013) 623-627.

2.S.J.Richard Prabakar、Yun-Hwa Hwang、Eun Gyoung Bae、Dong Kyu Lee、 Myoungho Pyo, " Graphene oxide as a corrosion inhibitor for the aluminum Current collector in lithium ion batteries is [as the corruption for the aluminium collector in lithium ion battery The graphene oxide of corrosion inhibitor] ", Carbon [carbon], 52 (2013) 128-136.

3.Yang Li et al. people, 104600320 A of China Patent Publication No. CN (on May 6th, 2015).

4.Zhaoping Liu et al. people, (Ningbo Institute of Materials and Energy, China [in State's Ningbo material and Energy Research Institute]), WO 2012/151880A1 (on November 15th, 2012).

5.Gwon,H.;Kim,H-S;Lee,KE;Seo,D-H;Park,YC;Lee,Y-S;Ahn,BT;Kang,K; " Flexible energy storage devices based on graphene paper [the flexible energy based on graphene paper Measure storage device] ", Energy and Environmental Science [energy and environment science], 4 (2011) 1277- 1283。

6.Ramesh C.Bhardwaj and Richard M.Mank, " Graphene current collectors in Batteries for portable electronic devices is [for the graphene in the battery of portable electronic device Collector] ", 20130095389 A1 of US, on April 18th, 2013.

Currently, there are three types of different forms for graphene collector: the substrate [bibliography 1-4] of graphene coating, stand alone type Then metal loses for graphene paper [bibliography 5] and the chemical vapor deposition (CVD) being catalyzed by transition metal (Ni, Cu) The single layer graphene film [bibliography 6] carved and produced.

In the preparation of the substrate of graphene coating, by graphene oxide (GO) or the graphene oxide (RGO) of reduction On small isolated piece or platelet jet deposition to solid substrate (for example, plastic foil or Al foil).In graphene layer, structure list Member is isolated graphene film/platelet (typically length/width is 0.5-5 μm and with a thickness of 0.34-30nm), the graphite Alkene piece/platelet combines [bibliography 1,3 and 4] typically via adhesive resin such as PVDF.Although individual graphene Piece/platelet can have relatively high conductivity (in described 0.5-5 μm of limitation), but gained graphene-adhesive resin Composite layer is relative mistake (typically < 100S/cm and more typically < 10S/cm) in terms of conductivity.In addition, using bonding Another purpose of agent resin is integrated to graphene-adhesive composite layer on substrate (for example, Cu foil);It means that There are adhesive resin (adhesive) layers between Cu foil and the graphene-adhesive composite layer.Unfortunately, this adhesive tree Rouge layer is electrical isolation and the ill-effect of generation seems fully to be ignored by work at present person.

Although Prabakar et al. [reference paper 2] does not appear to be formed using adhesive resin coated with discrete oxidation The aluminium foil of graphene film, but Al foil the problem of having its own of this graphene oxide coating.It is well known in the art to be, alumina Object (Al2O3) be easy to be formed on the surface of aluminium foil, and this aluminum oxide or aluminium oxide cannot be removed with acetone or alcohol cleaning Passivation layer.What this al oxide layer was not only electrically and thermally to insulate, and actually certain form of electrolyte is not tolerated. For example, most common lithium ion battery electrolyte is dissolved in the LiPF in organic solvent6.Trace H in this electrolyte2O may Trigger it is a series of be related to being formed the chemical reactions of HF (high corrosiveness acid), the HF be easy to decompose the al oxide layer and Continue to corrode Al foil and consumes electrolyte.Capacity attenuation typically becomes brighter after 200-300 charge-discharge cycles It is aobvious.

It is prepared by GO or RGO piece/platelet that free-standing graphene paper suspends in water typically via vacuum assisted filtration. In free-standing paper, structural unit is the isolated graphene film/platelet loosely to overlap.Again, although individually Graphene film/platelet can have relatively high conductivity (in described 0.5-5 μm of limitation), but gained graphene paper has Low-down conductivity;Such as 8,000S/m or 80S/cm [bibliography 5], than the conductivity (8x10 of Cu foil5S/cm) low 4 A order of magnitude.

It several is mainly asked in the presence of relevant to most common production method (i.e. chemical oxidation/the intercalation method) of graphene Topic:

(1) the method is needed using a large amount of several undesirable chemicals, such as sulfuric acid, nitric acid and potassium permanganate Or/and sodium chlorate.

(2) hot extruding needs high temperature (typically 800 DEG C -1,050 DEG C), and is therefore highly energy intensive method.

(3) the method needs very cumbersome washing and purification step.For example, typically being washed using the water of 2.5kg 1 gram of GIC is washed and recycled, the waste water for largely needing proper treatment is generated.

(4) products therefrom is graphene oxide (GO) platelet, is subjected to further electronation processing to reduce Oxygen content.Typically, or even after reduction, the conductivity of the conductivity of GO platelet still far below raw graphite alkene.In addition, reduction Program is often referred to using toxic chemical, such as hydrazine.

(5) in addition, the range for the intercalation solution amount being retained in after draining on thin slice to can be from 20 to 150 parts by weight molten Liquid/100 parts by weight of graphite flakes (pph), and more typically about 50 to 120pph.During high temperature puffing, protected by thin slice The remaining intercalation species that stay, which decompose, generates various undesirable sulfur-bearings and containing nitrogen compound (such as NOxAnd SOx).Stream Object needs expensive regulation program out, so as not to unfavorable environment influence.

The CVD process of catalysis for graphene production is related to true at a temperature of appropriate hydrocarbon gas is introduced 500 DEG C -800 DEG C In empty room.Under these stringent conditions, the appropriate hydrocarbon gas is decomposed, wherein the decomposition reaction by transition metal substrate (Ni or Cu it) is catalyzed.Then the Cu/Ni substrate is chemically etched away using strong acid, this is not environmental-friendly program.The entire mistake Journey is slow, tediously long and consume energy, and gained graphene be typically single-layer graphene or few layer graphene (up to 5 layers, because Its effect as catalyst is lost for following Cu/Ni layer).

Bhardwaj et al. [bibliography 6] suggests stacking multiple CVD- graphene films to 1 μm or several μm of thickness;So And this will need the hundreds of or thousands of films being stacked (each film typically 0.34nm to 2nm is thick).Although Bhardwaj Et al. claim " graphene can reduce manufacturing cost and/or increase battery battery core energy density ", but without present experiment Data support their claim.It is claimed with this on the contrary, CVD graphene is notoriously expensive process, and even single The CVD graphene film of layer will be significantly more more expensive than Cu foil or Al paillon, it is assumed that area is identical (for example, identical 5cm x 5cm). As the stacked body of Bhardwaj et al. hundreds of or thousands of single layers suggested or the graphene film of few layer will imply that than Cu foil collection Fluid is more expensive hundreds of or thousands of times.This cost will be excessively high.Further, hundreds of CVD graphenes in stacked body The relatively low conductivity of high contact resistance and CVD graphene between film will lead to high total internal resistance, so that using compared with film (relative to 10 μm of Cu foil, 1 μm of graphene stacked body) is become with any potential benefit for reducing battery core total weight and total volume It obtains in vain.Seem, the patent application [bibliography 6] of Bhardwaj et al. (being free of any data) only concept paper.

It is described above to be clearly shown, all three graphene enhancing or the collector based on graphene forms Performance used in battery or supercapacitor and cost requirement is not satisfied.Exist to the different kind of material for being used as collector Tight demand.

The present invention relates to a kind of new material, herein referred as height-oriented humic acid (HA) film (individually or with graphene group Close), it is chemically bonded to metal foil surface.Graphene used herein includes raw graphite alkene, graphene oxide, fluorographite Alkene, nitridation graphene, hydrogenation graphene, boron-doped graphene, the doped graphene of any other type and other types Chemical functionalization graphene.Quite unexpectedly with significant, this height-oriented HA or HA/ graphene mixture Film can be with thermal transition for highly conductive property graphite film.

Humic acid (HA) is that typically in the organic substance found in soil, and alkali (such as KOH) can be used from soil Middle extraction.HA can also be extracted from a kind of coal for being known as leonardite with high yield, and the leonardite is high oxidation type The lignite of formula.The HA extracted from leonardite contains there are many oxygen-containing group (such as carboxyl), and the group is located at similar graphite Molecular center (the SP of lonsdaleite structure of alkene2Core) perimeter.The material is produced with by strong acid oxidation of natural graphite Graphene oxide (GO) it is slightly similar.With by weight 5% to 42% typical oxygen content, (other essential elements are HA Carbon and hydrogen).After chemistry or thermal reduction, HA has by weight 0.01% to 5% oxygen content.In order to which right is wanted in the application The purpose of restriction is sought, humic acid (HA) refers to by weight from 0.01% to 42% entire oxygen content range.The humic of reduction Sour (RHA) is the HA of the specific type of the oxygen content with by weight 0.01% to 5%.

It has surprising been found that humic acid can be with metal foil when making its intimate surface contact with metal foil It learns and combines.Further it has surprising been found that, when suitably arranging and being packed together, humic acid molecule can be changed each other Connection is learned to obtain longer and broader humic acid piece.These humic acid molecules can also with graphene film (if there is and Suitably arrange and accumulate) it is connected chemically or combines.The thin metal foil of gained combination humic acid or graphite film is that electrolyte-is compatible , non-reacted, etch-proof, contact resistance is low, thermal conductivity, it is ultra-thin and light-weight so that battery or electricity Container is capable of providing higher output voltage, higher energy density, high magnification ability and much longer cycle life.

Summary of the invention

The present invention provides a kind of for combining height-oriented humic acid used in the battery or supercapacitor Metal foil collector.The present invention also provides a kind of by metal foil and one or two main surface for being integrated to the metal foil The collector that highly conductive property graphite film is constituted derived from humic acid.The present invention also provides the methods for generating these collectors.

Collector of the invention includes: (a) thin metal foil, and the thin metal foil has from 1 μm to 30 μm (preferably from 4 μm To 12 μm) thickness and two opposite but substantially parallel main surfaces;(b) at least one height-oriented humic acid (HA) Or the film (or highly conductive property graphite film of derivative film since then) of the mixture of HA and graphene film, the film chemical knot Close at least one of two opposite major surfaces of the metal foil.When individually being surveyed in the case where no thin metal foil When amount, thickness that the film or derivative graphite film of HA the or HA/ graphene mixture have from 10nm to 10 μm, by weight Count from 0.01% to 10% oxygen content, from 1.3 to 2.2g/cm3Phsyical density, be substantially parallel to each other and be parallel to institute It states the lonsdaleite plane of main surface orientation, 0.335 to 0.50nm interplanar spacing between lonsdaleite plane, be greater than 250W/mK The thermal conductivity of (more typically > 500W/mK) and the conductivity for being greater than 800S/cm (more typically > 1,500S/cm).

Preferably, each of described two opposite major surfaces and such humic acid or HA/ graphene mixture Film or by heat treatment generate derivative since then film graphite film be chemically combined.It is further preferred that one or two HA or HA With the film (or derivative graphite film) of both graphenes be chemically bonded to one or two opposite major surfaces of metal foil without Use adhesive or adhesive.If this adhesive is selected from inherently conductive polymer, pitch, nothing using adhesive The conductive material of setting carbon or carbide resin (polymerization carbon).Preferably, the thin metal foil has from 4 to 12 μm of thickness.Also Preferably, the film or graphite film of the humic acid or HA/ graphene mixture have the thickness from 20nm to 2 μm.

For the collector, it is preferable that metal foil be selected from Cu, Ti, Ni, stainless steel, Al foil, or combinations thereof.Preferably, Main surface does not contain passive metal oxide skin(coating) on it (such as does not have aluminium oxide Al on Al foil surface2O3)。

Preferably, the film of the HA or HA/ graphene mixture or graphite film as derived from it have by weight from 1% to 5% oxygen content.It is further preferred that the film or graphite film as derived from it have oxygen content less than 1%, Interplanar spacing less than 0.345nm and the conductivity not less than 3,000S/cm.It is highly preferred that the film or being spread out by it Raw graphite film has the oxygen content less than 0.1%, the interplanar spacing less than 0.337nm and not less than 5,000S/cm's Conductivity.It is more preferred still that the film or graphite film as derived from it have oxygen content no more than 0.05%, are less than The interplanar spacing of 0.336nm inlays latitude of emulsion value and the conductivity not less than 8,000S/cm no more than 0.7.Even more Preferably, the film or graphite film as derived from it have the interplanar spacing less than 0.336nm, inlaying no more than 0.4 Latitude of emulsion value and conductivity greater than 10,000S/cm.

It is highly preferred that the film or graphite film as derived from it of HA the or HA/ graphene mixture show and are less than The interplanar spacing of 0.337nm and latitude of emulsion value is inlayed less than 1.0.Most preferably, the film or graphite film as derived from it It shows the degree of graphitization not less than 80% and/or inlays latitude of emulsion value no more than 0.4.

In certain embodiments, the film of the HA or HA/ graphene mixture is obtained in the following manner: being controlled in orientation Under the influence of stress processed by the suspension of HA or HA and the mixture of graphene film deposit at least one described main surface with The layer of HA or HA and graphene film mixture are formed, and is then heat-treated under 500 DEG C of heat treatment temperature from 80 DEG C to 1 The layer.It is highly preferred that the heat treatment temperature is from 80 DEG C to 500 DEG C and even more preferably from 80 DEG C to 200 DEG C.

It is integrated to the height-oriented film or graphite as derived from it of the HA or HA/ graphene of following collector Film typically contains the humic acid and graphene planes that the chemically combined humic acid molecule being parallel to each other or chemistry merge, and such as schemes Shown in 3 (C).Preferably, the film is the continuous length film that the length that has is not less than 1cm not less than 5cm and width, and This film is made of roll-to-roll (roll-to-roll) method.

Preferably, when the individually measurement (as the free-standing layer that metal foil is not present), HA the or HA/ graphene mixing The film of object or graphite film as derived from it have greater than the phsyical density of 1.6g/cm3, and/or strong greater than the stretching of 30MPa Degree.It is highly preferred that the film or graphite film as derived from it have the physics for being greater than 1.8g/cm3 close when independent measurement Degree, and/or the tensile strength greater than 50MPa.Most preferably, when independent measurement, the film or graphite film as derived from it With greater than 2.0g/cm3Phsyical density, and/or tensile strength greater than 80MPa.

The present invention also provides a kind of lithium rechargeable battery or lithium ion batteries, contain collector conduct of the invention Anode collector and/or cathode current collector.The lithium rechargeable battery can be lithium-sulphur battery core, lithium-selenium battery core, lithium sulphur/selenium Battery core, lithium-air battery core, lithium-graphene battery core or lithium-carbon battery core.

The present invention also provides a kind of capacitor, the capacitor contain collector of the invention as anode collector or Cathode current collector, the capacitor are symmetrical supercapacitor, asymmetric super capacitor electric core, hybrid super capacitor Device-battery battery core or lithium-ion capacitor battery core.

It is height-oriented for combining used in the battery or supercapacitor for generating that the present invention also provides one kind Humic sorrel metal foil collector method.The described method includes:

(a) it prepares humic acid (HA) or chemical functionalization humic acid (CHA) piece is scattered in dispersion in liquid medium, In, the HA piece contain by weight of from more than 5% oxygen content or the CHA piece contain by weight of from more than 5% non-carbon member Cellulose content;

(b) HA the or CHA dispersion is distributed and is deposited at least one main surface of metal foil in the table The wet layer of HA or CHA is formed on face, wherein the distribution and deposition procedure include that the dispersion is made to be subjected to orientation induced stress;

(c) liquid medium is removed partially or even wholly from the wet layer of the HA or CHA to be formed with lonsdaleite The interplanar spacing d of plane and the 0.4nm to 1.3nm as passed through X-ray diffraction measure002HA or CHA layers of drying;And

(d) described dry HA or CHA layers lasting time enough is heat-treated under the first heat treatment temperature higher than 80 DEG C Section is to generate the metal foil collector of the height-oriented humic sorrel of the combination, wherein the humic acid film contains substantially phase HA the or CHA piece of interconnection, merging or thermal reduction mutual parallel and that be chemically bonded to and be parallel to the main surface, and The humic sorrel, which has, is not less than 1.3g/cm3Phsyical density, at least the thermal conductivity of 250W/mK, and/or be not less than 500S/ The conductivity of cm.The method may further include the HA or CHA of the merging or reduction after the step (d) The step of humic acid membrane pressure contracting.

The method may include other steps (e): in the second heat treatment temperature for being higher than first heat treatment temperature The metal foil that the combination humic sorrel is further heat-treated under degree continues time enough section to generate the gold for combining graphite film Belong to foil collector, wherein the graphite film has the interplanar spacing d less than 0.4nm002Oxygen by weight less than 5% contains Amount or non-carbon element content;(f): compressing the graphite film to generate and have not less than 1.3g/cm3Phsyical density, at least The thermal conductivity of 500W/mK, and/or highly conductive property graphite film not less than the conductivity of 1,000S/cm.The highly conductive property Graphite film preferably has from 5nm to 20 μm but the thickness more preferably from 10nm to 2 μm.

HA or CHA dispersion can further contain graphene film dispersed therein or molecule, and HA and graphene Or the ratio of CHA and graphene is from 1/100 to 100/1, wherein graphene is selected from raw graphite alkene, graphene oxide, reduction Graphene oxide, fluorinated graphene, bromination graphene, iodate graphene, boron-doped graphene, adulterate nitrogen graphene, Chemical functionalization graphene, or combinations thereof.The method may include other steps (e): will be the merging or reduction Further heat treatment continues foot to the humic sorrel of HA or CHA under the second heat treatment temperature for being higher than first heat treatment temperature Enough periods are to generate the interplanar spacing d having less than 0.4nm002Oxygen content or non-carbon member by weight less than 5% The graphite film of cellulose content;With step (f): compressing the graphite film to generate and have not less than 1.6g/cm3Phsyical density, extremely The thermal conductivity of 700W/mK, and/or the highly conductive property graphite film not less than the conductivity of 1,500S/cm less.

In certain embodiments, HA or CHA piece is to be in the amount for being enough to be formed liquid crystalline phase in liquid medium.Preferably, Dispersion contains the HA or CHA for the first volume fraction being scattered in the liquid medium, and first volume fraction is more than Critical volume fraction (the V that liquid crystalline phase is formedc), and the dispersion is concentrated to reach and be greater than first volume fraction The second volume fraction of HA or CHA, to improve HA or CHA piece orientation.Preferably, the first volume fraction is equivalent to HA or CHA exists By weight from 0.05% to 3.0% weight fraction in the dispersion.Before the step (b), it can will disperse Body is concentrated into containing the by weight of from more than 3.0% but HA or CHA that are scattered in liquid medium less than 15%.

In some embodiments, dispersion, which further contains, is dissolved in the liquid medium or attaches to HA's or CHA Polymer.

The CHA contains the chemical functional group selected from following item: polymer, SO3H、COOH、NH2、OH、R'CHOH、 CHO, CN, COCl, halogen root, COSH, SH, COOR', SR', SiR'3、Si(--OR'--)yR'3-y、Si(--O--SiR'2--)OR'、 R"、Li、AlR'2、Hg--X、TlZ2And Mg--X;Wherein, y is equal to or the integer less than 3, R' are hydrogen, alkyl, aryl, cycloalkanes Base or aralkyl, cyclophane base or poly- (alkyl ether), R " be fluoro-alkyl, fluorinated aryl, fluoro naphthenic base, fluoroaralkyl or Cyclophane base, X are halogen roots, and Z be carboxylate radical or trifluoroacetic acid root, or combinations thereof.

Graphene film (if present) can contain chemical functionalization graphene, and the chemical functionalization graphene contains choosing From the chemical functional group of following item: polymer, SO3H、COOH、NH2, OH, R'CHOH, CHO, CN, COCl, halogen root, COSH, SH, COOR'、SR'、SiR'3、Si(--OR'--)yR'3-y、Si(--O--SiR'2--)OR'、R"、Li、AlR'2、Hg--X、TlZ2With Mg--X;Wherein, y is equal to or the integer less than 3, R' are hydrogen, alkyl, aryl, naphthenic base or aralkyl, cyclophane base or poly- (alkyl ether), R " are fluoro-alkyl, fluorinated aryl, fluoro naphthenic base, fluoroaralkyl or cyclophane base, and X is halogen root, and Z is Carboxylate radical or trifluoroacetic acid root, or combinations thereof.

Preferably, liquid medium is made of the mixture of water or water and alcohol.Alternatively, liquid medium contains selected from following The non-aqueous solvent of item: polyethylene glycol, propylene glycol, alcohol, sugar alcohol, polyglycereol, glycol ethers, solvent amine-based, is based on ethylene glycol Solvent, alkylene carbonates, organic acid or the inorganic acid of amide.

Second heat treatment temperature can be higher than 1,500 DEG C, persistently be enough interplanar spacing d002It is decreased to less than 0.36nm Value and oxygen content or non-carbon element content are decreased to a period of time by weight less than 0.1%.Specifically, the second heat Treatment temperature can be from 1,500 DEG C to 3,200 DEG C.

The method is preferably roll-to-roll or reel-to-reel (reel-to-reel) method, wherein step (b) include will be golden Belong to foil piece be fed to crystallizing field from roller, by the layer of HA or CHA dispersion deposit at least one main surface of metal foil with It is formed on the wet layer of HA or CHA dispersion, dry HA or CHA dispersion is to form the drying being deposited in metal foil surface HA or CHA layers, and the HA or CHA layers of metal foil deposited is collected on collecting drum.

In certain embodiments, temperature of first heat treatment temperature within the scope of 100 DEG C -1,500 DEG C, and height The humic sorrel of orientation has the oxygen content less than 2.0%, the interplanar spacing less than 0.35nm, is not less than 1.6g/cm3Object Manage density, at least thermal conductivity of 800W/mK, and/or the conductivity not less than 2,500S/cm.In other embodiments, the first heat Treatment temperature is included in the temperature within the scope of 1,500 DEG C -2,100 DEG C, and height-oriented humic sorrel, becomes highly conductive Property graphite film, have the oxygen content less than 1.0%, the interplanar spacing less than 0.345nm, at least 1, the thermal conductivity of 000W/mK, And/or the conductivity not less than 5,000S/cm.

In some embodiments, the first and/or second heat treatment temperature includes the temperature greater than 2,100 DEG C, and highly Conductive graphite film has the oxygen content no more than 0.1%, spacing, inlaying no more than 0.7 between the graphene less than 0.340nm The thermal conductivity of latitude of emulsion value, at least 1,300W/mK, and/or conductivity not less than 8,000S/cm.If the second heat treatment temperature Comprising being not less than 2,500 DEG C of temperature, then highly conductive property graphite film has spacing between the graphene less than 0.336nm, less Latitude of emulsion value, the thermal conductivity greater than 1,500W/mK are inlayed, and/or greater than the conductivity of 10,000S/cm in 0.4.Degree of graphitization 80% can be not less than, and inlay latitude of emulsion value less than 0.4.

Typically, HA or CHA piece has maximum original length, and height-oriented humic sorrel includes the length having Greater than HA the or CHA piece of the maximum original length.This means that some humic acid molecules in a manner of edge-to-edge with other HA Molecule merges, to increase the length or width of planar molecule or piece.The heat treatment step (e) causes HA or CHA piece and other HA or CHA piece is connected chemically, merges or is chemically combined to form graphite-structure with graphene film.Highly conductive property graphite Film is the polycrystalline graphite alkene structure with preferred crystallite orientation as measured by the X-ray diffraction method.

The method typically results in form height-oriented graphite film, and the height-oriented graphite film, which has, is greater than 5, The conductivity of 000S/cm, is greater than 1.9g/cm at the thermal conductivity greater than 800W/mK3Phsyical density, strong greater than the stretching of 80MPa Degree, and/or the elasticity modulus greater than 60GPa.Further typically, height-oriented graphite film has greater than 8,000S/cm's Conductivity, is greater than 2.0g/cm at the thermal conductivity greater than 1,200W/mK3Phsyical density, the tensile strength greater than 100MPa and/ Or the elasticity modulus greater than 80GPa.Using being higher than 1,500 DEG C of final heat treatment temperature (first or second heat treatment temperature), Height-oriented graphite film has the conductivity greater than 12,000S/cm, the thermal conductivity greater than 1,500W/mK, is greater than 2.1g/cm3 Phsyical density, the tensile strength greater than 120MPa, and/or the elasticity modulus greater than 120GPa.

Detailed description of the invention

Fig. 1 (A) is shown for producing expanded graphite product (soft graphite foil and Flexible Graphite Composites) and pyrolysis stone The flow chart of the method for the various prior arts of black (bottom part).

Fig. 1 (B) in the form of graphene paper or film for producing isolated graphene film and graphene or graphite oxide The method of the aggregation of alkene piece.

Fig. 1 (C) in the form of graphene paper or film for producing isolated graphene film and graphene or graphite oxide The method of the aggregation of alkene piece.

The SEM image of the cross section of Fig. 2 soft graphite foil has it illustrates many and is not parallel to the soft graphite foil The graphite flake of the orientation of surface plane, and many defects are also shown, kink or folding thin slice.

The SEM image of the HOGF of Fig. 3 (A) HA liquid crystal derived, plurality of lonsdaleite plane are seamlessly merged into extensible Several tens cm is wide or grows the similar of the continuous length of (50 μm of width of the HOGF of 10-cm wide are illustrated only in this SEM image) The sheet or layer of graphene;

Fig. 3 (B) is using paper technology (for example, vacuum assisted filtration) by graphene oxide sheet/platelet of discrete reduction The SEM image of the cross section of the ordinary graphite alkene paper of preparation.It (is not one that described image, which shows many and is folded or interrupts, Change) discrete graphene film, have and be not parallel to film/paper surface orientation, and there is many defects or flaw;

Fig. 3 (C) height-oriented humic acid molecular film chemistry is merged to form high-sequential and conductive graphite The schematic diagram of film.

HOGF, HA derived from HOGF, GO derived from the HA/GO that Fig. 4 (A) is drawn as the function of final heat treatment temperature spread out The heat conductivity value of raw HOGF and FG foil;

HOGF derived from HOGF, HA derived from the HA/GO that Fig. 4 (B) is drawn as the function of final HTT and polyamides are sub- The heat conductivity value of HOPG derived from amine;And

HOGF, HA derived from HOGF, GO derived from the HA/GO that Fig. 4 (C) is drawn as the function of final heat treatment temperature spread out The conductivity value of raw HOGF and FG foil.

Spacing between graphene planes in HOGF derived from the HA that Fig. 5 (A) passes through X-ray diffraction measurement;

Oxygen content in HOGF derived from Fig. 5 (B) HA;

Correlation between Fig. 5 (C) graphene between spacing and oxygen content;And

HOGF, HA derived from HOGF, GO derived from the HA/GO that Fig. 5 (D) is drawn as the function of final heat treatment temperature spread out The heat conductivity value of raw HOGF and FG foil.

The thermal conductivity for the HOGF sample that the function of ratio of the Fig. 6 as GO piece in HA/GO suspension is drawn.

HOGF, HA derived from HOGF, GO derived from the HA/GO that Fig. 7 (A) is drawn as the function of final heat treatment temperature The tensile strength values of the graphene oxide paper of derivative HOGF, soft graphite foil and reduction;

HOGF and HA derived from HOGF, GO derived from the HA/GO that Fig. 7 (B) is drawn as the function of final heat treatment temperature The stretch modulus of derivative HOGF.

The thermal conductivity of height-oriented film derived from tri- kinds of HA of Fig. 8;A kind of HA removed by heat treatment from glass surface Film obtains, a kind of to deposit and be integrated to the surface Ti in heat treatment, and one kind deposits in heat treatment and is integrated to Cu foil table Face.

The discharge capacity value of Fig. 9 (A) three kinds of Li-S battery cores, the individually function as charge/discharge cycle number;First electricity Core has the Cu foil respectively as the combination HA of anode and cathode collector and combines the Al foil of HA;Second battery core (the prior art Battery core) have respectively as anode and cathode collector GO/ resin coating Cu foil and GO coating Al foil (do not lose in advance It carves);Third battery core (battery core of the prior art) has Cu foil anode collector and Al foil cathode current collector.

The Ragone curve graph of Fig. 9 (B) three kinds of battery cores below: the first battery core has respectively as anode and cathode collector Combination HA Cu foil and combine HA Al foil;Second battery core (battery core of the prior art) has respectively as anode and cathode collection The Cu foil of the GO/ resin coating of fluid and the Al foil (not having pre-etched) of GO coating;Third battery core (battery core of the prior art) tool There are Cu foil anode collector and Al foil cathode current collector.

The battery core capability value of three kinds of magnesium metal battery cores of Figure 10 or less: the first battery core has respectively as anode and cathode afflux The Cu foil of the combination HA of body and the Al foil for combining HA;Second battery core (battery core of the prior art) has respectively as anode and cathode The Cu foil of the GO/ resin coating of collector and the Al foil (not having pre-etched) of GO coating;Third battery core (battery core of the prior art) With Cu foil anode collector and Al foil cathode current collector.

Specific embodiment

The present invention provides a kind of for combining the metal foil film of humic acid used in the battery or supercapacitor Collector (for example, as Fig. 1 (C) is schematically shown).In a preferred embodiment, the collector includes: (a) independent Formula, non-supported type thin metal foil (214 in Fig. 1 (C)), the thin metal foil have thickness and two phases from 1 μm to 30 μm Anti- but substantially parallel main surface;(b) being chemically bonded at least one of described two opposite main surfaces (does not make In the case where with adhesive or adhesive) humic acid (HA) or HA/ graphene mixture film 212.Fig. 1 (C) is only shown One main surface of metal foil 214 is combined with the film 212 of HA or HA/ graphene mixture.It is preferable, however, that opposite Main surface also (is not shown) in conjunction with the film of HA or HA/ graphene mixture in Fig. 1 (C).As for by battery/super electricity Container is electrically connected to the end pole of external circuit, and metal tabs 218 typically by melting welding or are soldered to metal foil 214.

As shown in Fig. 1 (C), the preferred embodiment of the present invention is the metal foil collector in conjunction with HA, wherein HA or There is no adhesive resin layer or passivation al oxide layers between the film and Cu foil or Al foil of HA/ graphene mixture.Compared to it Under, as schematically shown in Fig. 1 (B), the metal foil collector of the graphene of prior art coating is typically and must Ground needs the adhesive resin layer between graphene layer (graphene-resin composite materials) and metal foil (for example, Cu foil).? Al foil [Prabakar et al. of the graphene coating of the prior art;Bibliography 2] in the case where, graphene layer and Al metal foil Between there is naturally passivation aluminum oxide (aluminium oxide) layer.This is because well-known following facts: when manufacture and exposure When room air, aluminium foil always forms passivation al oxide layer on Al foil surface.Not by the easy clean of acetone or alcohol This alumina layer can be removed.As by set forth in paragraph below, adhesive resin or al oxide layer are (even if be as thin as only Presence 1nm) has tremendous influence to the contact resistance increased between graphene layer and metal foil.We this are surprisingly found that Ignored completely by the worker of all prior arts, and therefore, the metal foil of the graphene coating of the prior art is unsatisfactory for lithium The performance and cost requirement of battery or current collector of super capacitor.

Make the highly significant that humic acid piece and the main surface of Cu, Ni, steel or Ti foil directly contact and unexpected advantage Be following viewpoint: HA molecule can be integrated to these metal foils well under processing conditions of the invention, without using External resin binder or adhesive (therefore, not dramatically increasing contact resistance).These processing conditions include making HA (or HA With the mixture of graphene) arrangement well and then in 80 DEG C of -1,500 DEG C of (more allusion quotations in metal foil surface of molecule or piece Type and hopefully 80 DEG C -500 DEG C and most typically and hopefully 80 DEG C -200 DEG C) at a temperature in the range of be heat-treated two Layer structure.Optionally, but non-preferentially, heat treatment temperature can be up to 1,500 DEG C -3, and 000 DEG C (assuming that metal foil can be born So high temperature).

In the case where the collector based on aluminium foil, these processing conditions are preferably included in front of coating and being combined with HA will Passivation al oxide layer chemically etches away, and is then heat-treated under the conditions of comparable temperature described above.It is alternative Ground, HA molecule can be prepared with acid state, it is characterised in that there is high oxygen content (to reflect-OH and-the COOH base of a large amount Group) and with the pH value less than 5.0 (preferably < 3.0 and even more preferably < 2.0).Al foil can be made to immerse HA solution bath In, wherein acidic environment eliminates passivation Al naturally2O3Layer.When Al foil is revealed from bath, HA molecule or piece are naturally Clean, etched Al foil surface is adhered to, Al foil surface is effectively prevented and is exposed to (therefore, Al foil in open air Without passivation Al between surface and HA layers2O3Layer and no increased contact resistance).It is never disclosed or builds before this strategy It discussed.

Other than the chemical bonding ability of HA layer and the chemical etching ability of HA solution of the invention, combination of the invention The film of gained HA or HA/ graphene mixture in the metal foil of HA have thickness from 10nm to 10 μm, by weight from Spacing between 0.1% to 10% oxygen content, the graphene planes of 0.335nm to 0.50nm, from 1.3 to 2.2g/cm3Physics it is close Degree, all HA and graphene film (if present) are oriented to and are substantially parallel to each other and are parallel to main surface, when not thin In the case where metal foil when independent measurement, shows the thermal conductivity greater than 500W/mK and/or be greater than the conductivity of 1,500S/cm. The film of this HA or HA/ graphene is chemically inert and provides the highly effective guarantor for resisting the corrosion of following metal foil Sheath.

Now, let us detailed examination such as the all-in resistance (including contact resistance) in the three-decker shown in Fig. 1 (B) Size.Electronics in graphene layer 202 (layer 1) must move around in this layer, move through adhesive resin or passivation Alumina layer 206 (layer 2), and it is then mobile to terminal tab 208 in metal foil layer 204 (layer 3).For the sake of simplicity, I Will only consider to move through the thickness of the graphene layer, described adhesive/passivation layer thickness and described for electronics The all-in resistance of the thickness of metal foil layer.Electronics movement in the face of both graphene or metal foil on direction is rapid and low electricity Resistance;Therefore, this resistance is ignored in calculating of the invention.

The thickness direction resistance of conductor sheet film is given by: R=(1/ σ) (t/A), wherein conductor described in A=is transversal Area (length x width), the thickness of conductor described in t=,And(material is normal Number).Collector containing the coating of the graphene of adhesive or passive metal oxide skin(coating), which can be considered as having, to be electrically connected in series Graphene film, interfacial bonder resin layer (or passive oxidation aluminium layer) and metal foil layer three-decker (Fig. 1 (B)).

All-in resistance is the summation of the resistance value of three layers: R=R1+R2+R31(t1/A1)+ρ2(t2/A2)+ρ3(t3/ A31/ σ of)=(1)(t1/A1)+(1/σ2)(t2/A2)+(1/σ3)(t3/A3), wherein ρ=resistivity, σ=conductivity, t=thickness, And A=layers of area, and approximatively, A1=A2=A3.Scanning electronic microscope examination disclose, described adhesive resin or Passive oxidation aluminium layer is typically 5-100nm thick.The resistivity and aluminium oxide of most common adhesive resin (PVDF) (Al2O3) resistivity typically 1013-1015In the range of ohm-cm.Assuming that A1=A2=A3=1cm2, graphene layer Thickness direction electricalresistivityρ1=0.1 ohm-cm, adhesive or alumina layer electricalresistivityρ2=1 × 1014Ohm-cm, and And metal foil layer resistivity is ρ3=1.7 × 10-6Ohm-cm (Cu foil) or ρ3=2.7 × 10-6Ohm-cm (Al foil). It is also supposed that following optimum condition, wherein Cu foil or Al foil thickness=6 μm, graphene layer thickness=1 μm, and adhesive resin layer Thickness is only 0.5nm (actually it is from 5nm to 100nm).Then the all-in resistance of the three-decker will be 5 × 106Ohm is simultaneously And whole conductivity will be down to 1.4 × 10-10S/cm (referring to the first data line in the following table 1).If we assume that adhesive tree Rouge layer is 10nm thickness, and the all-in resistance of the three-decker will be 1 × 108Ohm and whole conductivity will be down to 7.0 × 10- 12S/cm (referring to the 4th data line in the following table 1).Such 3 layers of composite construction will not be for the good of battery or supercapacitor Good collector, because high internal resistance will imply that the inside heat production of low output voltage and a large amount.For based on Ni foil, Ti foil and not The collector of rust steel foil, observed similar result (the data line 7-10 in table 1).

Table 1:

In contrast, if there is no adhesive resin or alumina layer (t2=0) (the feelings of collector such as of the invention Condition), have 1.0 × 10 in conjunction with the all-in resistance of the Cu foil of graphene oxide-5Ohm value (with containing 1- μm of adhesive resin layer The 1.0 × 10 of 3-tier architecture+7Ohm is compared).Refer to the following table 2.This represents the difference of 12 orders of magnitude (not being 12 times)!With phase The 7.0 × 10 of the 3-tier architecture answered-11S/cm is compared, and for 2 layers of structure of the invention, conductivity will be 7.0 × 10+1S/cm.Again Once, difference is 12 orders of magnitude.In addition, we have found that, compared with the collector based on graphene of the prior art, with The lithium battery and supercapacitor that the metal foil collector of combination graphene oxide of the invention is characterized always show higher Voltage output, higher energy density, higher power density, more stable charge-discharge cycles respond and continue more Long without capacity attenuation or etching problem.

Table 2:

Hereinafter, the description for presenting humic acid and graphene is two kinds in the film coated on metal foil Main component.

Block natural flake graphite is 3-D graphite material, wherein each particle by multiple crystal grain (crystal grain be graphite monocrystalline or Crystallite) it constitutes, these crystal grain have the crystal boundary (amorphous or defect area) for defining neighbouring graphite monocrystalline.Each crystal grain by putting down each other Multiple graphene planes of row orientation are constituted.Graphene planes in graphite microcrystal are by occupying the carbon atom structure of two-dimentional hexagoinal lattice At.In given crystal grain or monocrystalline, graphene planes are stacked at the direction crystallography c- (perpendicular to graphene planes or basal plane) And it is combined by Van der Waals force.Although all graphene planes in a crystal grain be it is parallel to each other, typically one The graphene planes in graphene planes and neighboring die in crystal grain are different in orientation.In other words, in graphite particle Different crystal grain orientation it is typically different from a crystal grain to another crystal grain.

Graphite monocrystalline (crystallite) is anisotropic in itself, wherein direction (crystallography a- axis or the b- axis direction) along basal plane The characteristic of measurement and the characteristic measured along crystallography c- axis direction (thickness direction) are dramatically different.For example, the thermal conductivity of graphite monocrystalline Rate (crystallography a- and b- axis direction) in basal plane can be up to about 1,920W/mK (theoretical value) or 1,800W/mK (experiment Value), but 10W/mK (typically less than 5W/mK) is less than along crystallography c- axis direction.Further, multiple in graphite particle Crystal grain or crystallite are typically orientated all along different directions.Therefore, the natural stone being made of multiple crystal grain of different orientation Black particle shows the average characteristics (i.e. typically < 100W/mK) between the two limiting values.

The composition graphene planes (typically 30nm-2 μm of width/length) of graphite microcrystal can be by extruding and from the graphite It extracts or is isolated to obtain the individual graphene film of carbon atom, premise is that overcoming interplanar Van der Waals force in crystallite.Six The isolation of square carbon atom, individual graphene film is commonly known as single-layer graphene.Graphene planes with 0.3354nm Between spacing in a thickness direction multilayer stone is commonly known as by the stacked body of multiple graphene planes that Van der Waals force combines Black alkene.Multi-layer graphene platelet has up to 300 layers of graphene planes (on thickness < 100nm) but more typically up to 30 graphene planes (on thickness < 10nm), be even more typically up to 20 graphene planes (on thickness < 7nm), And most typically it is up to 10 graphene planes (commonly known as lacking layer graphene in scientific circles).Single-layer graphene film and Multi-layer graphene piece is collectively referred to as " nano-graphene platelet " (NGP).Graphene film/platelet or NGP are and 0-D fullerene, 1-D The different a new class of carbon nanomaterial of CNT with 3-D graphite (2-D nano-sized carbon).

Early in 2002, our research group started raw graphite alkene material (isolated graphene oxide sheet) and The exploitation of related methods of production: (1) B.Z.Jang and W.C.Huang, " Nano-scaled Graphene Plates [nanoscale Graphene board] ", U.S. Patent number 7,071,258 (07/04/2006), the application submitted on October 21 in 2002;(2) " Process for Producing Nano-scaled Graphene Plates is [for producing nanoscale by B.Z.Jang et al. The method of graphene board] ", U.S. Patent Application No. 10/858,814 (06/03/2004);(3) B.Z.Jang, A.Zhamu and J.Guo, " Process for Producing Nano-scaled Platelets and Nanocomposites is [for giving birth to The method for producing nanoscale platelet and nanocomposite] ", U.S. Patent Application No. 11/509,424 (08/25/2006).History On, Brodie adds a part of potassium chlorate in slurry in fuming nitric aicd to graphite in first passage in 1859 and demonstrates oxidation The synthesis of graphite.In 1898, Staudenmaier was by using the concentrated sulfuric acid and fuming nitric aicd and during the reaction with more A equal portions addition chlorate improves this program.This small variation in program in single reaction vessel so that produce high The graphite for spending oxidation is significantly more practical.In 1958, Hummers reported most common method: by dense H2SO4 In use KMnO4And NaNO3Processing carrys out graphite oxide.However, the work of these early stages fails isolated and identifies complete extruding and separate Graphene oxide sheet.These researchs also fail to disclose the isolated of primary non-oxide single-layer or multi-layer graphene film.

In actual practice (such as shown in Fig. 1 (A)), NGP uses strong acid typically via by natural graphite particles 100 And/or oxidant intercalation is obtained with obtaining graphite intercalation compound 102 (GIC) or graphite oxide (GO).In graphene planes Between clearance space in chemical species or functional group presence for increasing spacing (d between graphene002, such as spread out by X-ray Penetrate measurement), thereby dramatically reduce the Van der Waals force that otherwise graphene planes keep together along c- axis direction.GIC Or GO most often by by natural graphite powder immerse sulfuric acid, nitric acid (oxidant) and another kind oxidant (such as potassium permanganate or Sodium perchlorate) mixture in produce.Gained GIC (102) is actually certain type of graphite oxide (GO) particle.Then The GIC or GO are repeatedly washed and rinsed to remove excessive acid in water, graphite oxide suspension or dispersion are generated, it should Suspension or dispersion contain be dispersed in water discrete and visually cognizable graphite oxide particle.In this rinsing step There are two processing routes later:

Route 1 is related to going water removal to obtain " expansible graphite " from suspension, is substantially a large amount of dry GIC or dry Dry graphite oxide particle.It is exposed to the constant temperature within the scope of typically 800 DEG C -1,050 DEG C about 30 seconds in expansible graphite When by 2 minutes, the fast volume that GIC is subjected to 30-300 times is expanded to form " graphite worm " (104), these graphite worms are respectively It is the aggregate of extruding but still the unsegregated graphite flake of major part of interconnection.

In route 1A, can by these graphite worms (expanded graphite or " interconnection/net of unsegregated graphite flake Network ") it recompresses to obtain flexible graphite platelet or foil (106), typically have in 0.1mm (100 μm) -0.5mm (500 μm) model Enclose interior thickness.Alternatively, it in order to produce the purpose of so-called " exfoliated graphite sheet " (108), can choose using low strong Air mill or cutter are spent simply to decompose the graphite worm, and the exfoliated graphite sheet mainly contains thicker than 100nm Graphite flake or platelet (therefore, according to definition be not nano material).These exfoliated graphite sheets can be made to paper-like stone Black felt (110).

Expanded graphite worm, exfoliated graphite sheet and graphite worm recompression substance (commonly referred to as flexible graphite platelet or Soft graphite foil) it is entirely 3-D graphite material, it is being fundamentally different from and is being clearly distinguished from 1-D nano-carbon material (CNT or CNF) or 2-D nano-carbon material (graphene film or platelet, NGP).Soft graphite (FG) foil may be used as radiating equipment Material, but show in the largest face of typically less than 500W/mK (more typically < 300W/mK) thermal conductivity and no more than 1, The face internal conductance rate of 500S/cm.These low conductivity values are the direct results of following item: the stone of many defects, fold or folding Black thin slice, interruption or gap and nonparallel thin slice (such as SEM image in Fig. 2) between graphite flake.Many thin slices (for example, misorientation of 20-40 degree) is angled with respect to each other with very big angle.

In route 1B, expanded graphite is made to be subjected to high-strength mechanical shearing (such as using ultrasonic generator, high shear mixing Device, high-intensitive air-jet mill or high-energy ball mill) with formed isolated single layer and multi-layer graphene piece (be referred to as NGP, 112), such as in our U.S. Application No. 10/858, disclosed in 814.Single-layer graphene can be as thin as 0.34nm, and multilayer Graphene can have the thickness of up to 100nm but more typically less than 20nm.It then can be by graphene film or platelet system At graphene paper or film (114).

For the purpose of the individual graphene oxide sheet of separation/isolation from graphite oxide particle, route 2 is required to oxidation Graphite suspension is ultrasonically treated.This is based on following viewpoint: the interval between graphene planes is from natural graphite 0.3354nm increases to the 0.6-1.1nm in highly oxidized graphite oxide, reduces significantly adjacent plane being maintained at one The Van der Waals force risen.It is separation, isolation or discrete to be formed that ultrasonic power can be enough further separation graphene planes piece Graphene oxide (GO) piece.It then can be by these graphene oxide sheets chemistry or thermal reduction to obtain " the graphite oxide of reduction Alkene " (RGO), typically there is 0.001%-10% by weight, more typically by weight 0.01%-5%, most typically And the oxygen content preferably by weight less than 2%.

In order to limit the purpose of claims hereof, NGP includes single layer and multilayer raw graphite alkene, graphene oxide Or discrete patch/platelet of the graphene oxide (RGO) of reduction.Raw graphite alkene has substantially 0% oxygen.RGO typically has There is the oxygen content of 0.001%-5% by weight.Graphene oxide (including RGO) can have 0.001%-50% by weight Oxygen.

It is noted that the soft graphite foil for electronic device thermal management applications (such as radiator material) is (logical Overcompression or roll-in expanded graphite worm obtain) there is following major defect: (1) as previously mentioned, soft graphite (FG) foil show Relatively low thermal conductivity out, typically < 500W/mK, and more typically < 300W/mK.By impregnating expanded graphite with resin, Gained composite material shows even lower thermal conductivity (typically < < 200W/mK, more typically < 100W/mK).(2) flexible Graphite foil, no resin are impregnated wherein or are coated on, the structural intergrity with low-intensity, Low rigidity and difference.It is soft The high tendentiousness that property graphite foil is torn makes them be difficult to handle during manufacturing radiator.In fact, soft graphite Piece (typically 50-200 μ m-thick) is such " softness ", is radiated to manufacture for fin so that they do not have enough rigidity The fin component material of device.(3) FG foil another is very delicate, be largely ignored or ignore but extremely The important high tendentiousness for being characterized in them and peeling off, graphite flake are easy to be detached from and shed to microelectronic device from FG piece surface Other parts.The thin slice (typically laterally having a size of 1-200 μm and thickness > 100nm) of these highly conductives may cause electricity The internal short-circuit of sub-device and failure.

Similarly, solid NGP (discrete patch/platelet including raw graphite alkene, GO and RGO), when use paper technology heap When accumulating film, film or the scraps of paper (114) at non-woven aggregation, high heat conductance is not shown typically, unless these piece/platelets Tightly packed and film/film/paper is ultra-thin (such as < 1 μm, be mechanically weak).This is reported in our early stages In U.S. Patent Application No. 11/784,606 (on April 9th, 2007).However, ultra-thin film or the scraps of paper (< 10 μm) are difficult to a large amount of lifes It produces, and is difficult to handle when attempting these films being combined into radiator material.In general, by the platelet of graphene, GO or RGO Manufactured paper-like structure or felt (for example, passing through those of the filtering technique preparation of the vacuum aided scraps of paper) show many defects, Fold or the graphene film of folding, interruption or gap and nonparallel platelet (such as the SEM in Fig. 3 (B) between platelet Image), lead to the thermal conductivity, low conductivity and low structural strength of relative mistake.Individually (do not have resin binder) from These paper or aggregation of scattered NGP, GO or RGO platelet also have flaky tendency, and conductive particle is distributed into air.

The graphite material of another prior art is pyrolytic graphite film, typically thinner than 100 μm.The technique starts from In 10-15Kg/cm under 400 DEG C -1,500 DEG C of carburizing temperature2Typical pressure under carbonized polymers film (for example, polyimides) Continue 10-36 hours to obtain char-forming material, is followed by 2,500 DEG C -3,200 DEG C in 100-300Kg/cm2Super-pressure Graphitization processing is carried out under power continues 1-24 hours to form graphite film.Such super-pressure is maintained under such ultra-high temperature Power is technically extremely challenging.This is difficult, slow, tediously long, energy consumption and extremely expensive technique.In addition, difficult always With by the polymer productions such as polyimides it is thinner than 10 μm or than 100 μ m-thicks pyrolytic graphite film.This thickness is relevant to ask Topic is that this kind of material is intrinsic, because they are difficult to be formed as the film (>100 μm) of ultra-thin (<10 μm) and thickness, while still keeping suitable When carbonization and be graphitized required for acceptable degree polymer chain orientation and mechanical strength.

The pyrolytic graphite of second of type is that carbon atom is then deposited to base by pyrolytic appropriate hydrocarbon gas in a vacuum It is generated on material surface.This vapor condensation of crackene is substantially chemical vapor deposition (CVD) technique.Particularly, height The pyrolytic graphite (HOPG) of orientation is the heat by making CVD deposition under very high temperature (typically 3,000-3,300 DEG C) Solution carbon is subjected to the material of uniaxial tension generation.Mechanical compression that this requirement is combined in protective atmosphere and simultaneous and superelevation The thermo-mechanical processi of temperature continues the extended period;It is very expensive, energy consumption, time-consuming and technical challenging Technique.The process requirement superhigh temperature equipment (having high vacuum, high pressure or high compression supply), which not only manufactures non- Chang Anggui and maintenance are got up very expensive and difficult.Even if using such extreme processing conditions, gained HOPG still has perhaps More defects, crystal boundary and misorientation (neighbouring graphene planes are not parallel to each other), lead to less than satisfactory face internal characteristic.Allusion quotation Type, the HOPG piece or block that best prepare typically contain there are many crystal grain of bad arrangement or crystal and a large amount of crystal boundary and Defect.

Similarly, report recently by appropriate hydrocarbon gas (such as C2H4) on the surface Ni or Cu catalysis CVD preparation graphite Alkene film (< 2nm) not instead of single crystal grain crystal, the polycrystalline structure with many crystal boundaries and defect.It is catalyst in Ni or Cu In the case where, Ni or Cu foil surface will be deposited to via the carbon atom that decomposing hydrocarbon gas molecule obtains at 800 DEG C -1,000 DEG C On to be formed as the piece of polycrystalline single layer or few layer graphene.The size of crystal grain is typically much less than 100 μm, and more typically Size is less than 10 μm.These graphene films (being optical clear and conduction) are intended for such as touch screen (to replace indium tin Oxide or ito glass) or semiconductor (with replace silicon, Si) etc. application.In addition, the CVD technique of Ni- or Cu- catalysis is not applicable In depositing more than 5 graphene planes (typically < 2nm), more than 5 graphene planes, Ni or Cu catalyst below cannot Any catalytic effect is provided again.There is no experimental evidence to show that the CVD graphene layer thicker than 5nm is possible.CVD graphene film and Both HOPG are very expensive.

It is described above to clearly illustrate that every kind of art methods or technique for producing graphene and graphite film are equal With main defect.Therefore, to having the characteristic necessary to collector (such as electric conductivity, thermal conductivity, to contact with metal foil Resistance), intensity and with the electrolyte phase capacitive of expected battery or supercapacitor in terms of it is comparable or more preferably one with graphene The new carbon nanomaterial of class exist there is an urgent need to.Must also be able to it is more cost effective, more rapidly, more scalability and more Environmental-friendly mode produces these materials.The production technology of such new carbon nanomaterial necessarily requires being not intended to for reduction amount Chemicals (or all eliminate these chemicals), shorten process time, the energy consumption of reduction, not wishing of reducing or eliminating The chemical species of prestige enter exhaust system (for example, sulfuric acid) or enter air (for example, SO2And NO2) discharge.

Humic acid (HA) is that typically in the organic substance found in soil, and alkali (such as KOH) can be used from soil Middle extraction.HA can also be extracted from a kind of coal for being known as leonardite, and the leonardite is the lignite of high oxidation pattern. The HA extracted from leonardite contains there are many oxygen-containing group (such as carboxyl), and the group is located in the molecule of similar graphene The heart (the SP of lonsdaleite structure2Core) perimeter.The material and the graphite oxide produced by strong acid oxidation of natural graphite Alkene (GO) is slightly similar.HA with by weight 5% to 42% typical oxygen content (other essential elements be carbon, hydrogen and Nitrogen).The example of the molecular structure of humic acid with various components (including quinone, phenol, catechol and saccharide part) is following (the source: Stevenson F.J., " Humus Chemistry:Genesis, Composition, Reactions [humic of scheme 1 Matter chemistry: origin, composition, reaction] ", John Wiley&Sons [John Wiley father and son publishing company], New York 1994) in give Out.

(scheme 1)

Non-aqueous solvent for humic acid includes polyethylene glycol, ethylene glycol, propylene glycol, alcohol, sugar alcohol, polyglycereol, glycol Ether, solvent amine-based, the solvent based on amide, alkylene carbonates, organic acid or inorganic acid.

The present invention also provides a kind of for producing height-oriented humic sorrel (with and without the graphite of outside addition Alkene piece) and humic acid derived from graphite film method, the film have with a thickness of from 2nm to 30 μm (more typically and preferably From 5nm to 10 μm, even more typically from 10nm to 2 μm), and phsyical density is not less than 1.3g/cm3(up to 2.2g/ cm3).This film is chemically bonded to metal foil surface.In certain embodiments, which comprises

(a) preparation have humic acid (HA) or chemical functionalization humic acid (CHA) piece be scattered in HA in liquid medium or The dispersion of CHA, wherein HA piece contains by weight of from more than 5% oxygen content or CHA piece contains by weight of from more than 5% Non-carbon element content;(in certain preferred embodiments, HA or CHA dispersion further contains graphene dispersed therein Piece or molecule, and the ratio of HA and graphene or CHA and graphene is from 1/100 to 100/1.These graphene films can select From raw graphite alkene, graphene oxide, the graphene oxide of reduction, fluorinated graphene, bromination graphene, iodate graphene, mix The graphene of miscellaneous boron, the graphene for adulterating nitrogen, chemical functionalization graphene, or combinations thereof.)

(b) HA the or CHA dispersion is distributed and is deposited at least one main surface of metal foil (such as Cu foil) To form the wet layer of HA or CHA, wherein the distribution and deposition procedure include that dispersion is made to be subjected to orientation induced stress;It is (this Tropism control stress (typically comprising shear stress) makes HA/CHA piece (or sheet molecule) and graphene film (if present) It can be arranged along the in-plane of metallic foil substrates surface (such as Cu foil).HA/CHA and graphite during subsequent heat treatment The appropriate arrangement of alkene piece is for being connected chemically between two or more HA/CHA pieces or between HA/CHA piece and graphene film Or merges and be necessary.)

(c) liquid medium is removed partially or even wholly from the wet layer of the HA or CHA to be formed with lonsdaleite The interplanar spacing d of plane and the 0.4nm to 1.3nm as passed through X-ray diffraction measure002HA or CHA layers of drying;And

(d) dry HA or CHA layers is heat-treated under the first heat treatment temperature higher than 80 DEG C and continues time enough section, To generate the height-oriented humic sorrel of containing the interconnection being substantially parallel to each other or combined HA or CHA piece.Humic acid Film is also chemically bonded to metal foil surface.These HA/CHA pieces are typically also heat-treated.The HA's or CHA of reduction is this Height-oriented humic sorrel can be subjected to the other step compressed against metal foil.

The method (with and without compression step) may include other step (e): by the merging and reduction HA or CHA humic sorrel be higher than first heat treatment temperature the second heat treatment temperature under further heat treatment continue Time enough section is to generate the interplanar spacing d having less than 0.4nm002Oxygen content or non-carbon by weight less than 5% The graphite film of constituent content;(f) graphite film (such as against Cu foil) is compressed to generate the height for being integrated to the metal foil Spend conductive graphite film.

In embodiment, step (e) includes being higher than the second heat treatment temperature of the first heat treatment temperature (typically > 300 DEG C) under be heat-treated height-oriented humic sorrel and continue for some time, the time is enough interplanar spacing d002Reduce to from The value of 0.3354nm to 0.36nm and oxygen content or non-carbon content are reduced to by weight less than 0.5%.Preferred real It applies in example, second (or final) heat treatment temperature includes at least one temperature selected from following item: 100 DEG C -300 DEG C of (A), (B) 300 DEG C -1,500 DEG C, 1,500 DEG C -2,500 DEG C of (C), and/or 2,500 DEG C -3,200 DEG C of (D).Preferably, the second heat treatment temperature Degree is included in 300 DEG C -1, and the constant temperature within the scope of 500 DEG C at least 1 hour, and then at 1,500 DEG C -3,200 DEG C of ranges Interior constant temperature is 1 hour at least other.

Typically, if the first and second heat treatment temperatures are below 1,500 DEG C, then height-oriented humic acid (HOHA) Film also contains the planar molecule of the feature for humic acid molecule.Height-oriented humic acid (HOHA) film contain chemical bonding and Combined lonsdaleite plane is HA/CHA or combined HA/CHA- graphene planes.These planes (have a small amount of oxygen-containing group The hexagonal structure carbon atom of group) it is parallel to each other.

If being exposed to 1,500 DEG C or higher heat treatment temperature (HTT) continue enough a period of times, then the HOHA film Typically no longer contain the humic acid molecule of any significant quantity, and essentially all HA/CHA piece/molecule has all been converted At the lonsdaleite plane of similar graphene or graphene oxide parallel to each other.The lateral dimension (length or width) of these planes It is huge, typically several times greater compared with the full-size (length/width) of beginning HA/CHA piece or even several orders of magnitude.This hair Bright HOHA be substantially it is all constitute similar graphene planes be substantially parallel to each other it is " huge lonsdaleite crystal " or " huge Plane is similar to graphene layer ".This is not to be found, develop or suggest in the past a kind of unique and new material that may be present.

Inherently a kind of very unique and novel material of the HA/CHA layer (HTT not > 1,500 DEG C HOHA film) of orientation Material unexpectedly has big cohesive force (self-bonding, auto polymerization and self-crosslinking ability).It does not pass previously in the prior art Award or imply these features.

The above paragraph is write to describe a type of collector, the collector will be by that will combine HA or HA/ graphite The metal film heat treatment of alkene mixture obtains for two layers or three-layered lamination object.HA or HA/ graphene layer is not removed from metal foil And individually (there is no metal foil) and be heat-treated.Gained collector does not contain adhesive resin or adhesive.This type claims herein For A type collector.Such collector can be heat-treated to the maximum temperature until the fusing point close to following metal foil. However, certain metal foils (such as Cu, Ti and steel) seem to be catalyzed the chemistry between HA piece or between HA and graphene even Connect, make it possible to be formed bigger HA/ graphene domain and fewer defects and cause higher thermal conductivity and conductivity and Structural intergrity (otherwise cannot achieve in the case where never calling more much higher heat treatment temperature).

The preparation of Type B collector describes in following two paragraph:

Alternatively, from (a) to (d) or procedure above (e) can carry out in the following manner: by HA or HA/ graphite The dispersion of alkene mixture deposits on plastic foil or glass surface, and after the liquid is removed, by gained desciccator diaphragm from plastic foil Or glass removing, so that then the film can be heat-treated at any desired temperature.Then height-oriented HA film (from After being heat-treated at a temperature of 80 DEG C to 1,500 DEG C) or derivative graphite film (from 1,500 DEG C to 3,200 DEG C at a temperature of heat at After reason) free-standing films are used as, one or two of metal foil (such as Cu or Al foil) is integrated to using adhesive resin or adhesive A main surface.With A type collector (wherein by the film of HA or HA/ graphene is deposited directly to metal foil surface and It is chemically bonded to this surface in the instance where such an adhesive is not utilized to prepare height-oriented HA film or highly pass as derived from it The property led graphite film) it compares, such Type B collector (obtaining at a temperature of comparable final heat treatment) has lower plane Interior thermal conductivity, lower plane internal conductance rate, higher interlayer contact resistance, and it is true inside battery or supercapacitor (being more easily layered) less durable in real liquid electrolyte environment.

In order to partly alleviate these problems, use is selected (such as to be commonly used for lithium battery than typical adhesive resin The adhesive material of electric conductivity is had more with PVDF, SBR etc. of supercapacitor industry).These include inherently conductive polymerization Object (such as polyaniline, polypyrrole, polythiophene etc.), pitch (such as isotropic pitch, mesophase pitch etc.), amorphous carbon (such as passing through chemical vapor infiltration) or carbide resin (it is heat-treated collector after free-standing graphite linings are integrated to metal foil, It is carbon binder by resin binder converted in-situ).

It is described below and is suitable for both A type and Type B collector.

For the HA of-OH containing significant quantity and/or-COOH group in certain edges in HA/CHA piece and/or plane Or CHA molecule (for example, there is the oxygen content by weight between 20% and 47%, preferably between 30% and 47%), Step (a) is needed HA/CHA piece or molecule dispersion in liquid medium, and the liquid medium can be the mixed of water or water and alcohol Close object.

When the volume fraction of HA/CHA or weight fraction are more than threshold value, discovery is dispersions obtained to contain liquid crystalline phase.It is preferred that Ground, before step (b), HA/CHA piece of the HA/CHA suspension (dispersion) containing initial volume score, the initial volume Score is more than the critical or threshold volume score for being used to form liquid crystalline phase.We have observed that such critical volume fraction allusion quotation The HA/CHA weight fraction being equivalent to type in from 0.2% to 5.0% range by weight of HA/CHA piece in dispersions.So And such low HA/CHA content range be not particularly suitable for using can scalable process (as cast and coating) formed it is desired thin Film.Ability by casting or coating production film is highly advantageous and is desired, because extensive and/or pour automatically Casting or application system are easy to get, and these known methods have the thin polymer film of consistently high-quality for producing It is reliable.Therefore, we continue the applicability that the dispersion containing the liquid crystalline phase based on HA/CHA is cast or coated Deeply and widely study.It was found that by masterbatched dispersion with by HA/CHA content from by weight 0.2% to 5.0% range increases to the range of by weight 4% to 16% HA/CHA piece, and we obtain height to be suitble to extensive life Produce the dispersion of thin graphene film.Most significantly and quite unexpectedly, liquid crystalline phase is not only retained, but also is often increased By force, so that HA/CHA piece is more feasible along being preferably orientated during casting or coating program.Particularly, containing pressing The HA/CHA piece in mesomorphic state of the HA/CHA piece of poidometer 4% to 16% is by usually used casting or coating method production There is the highest tendentiousness for becoming prone to orientation under the influence of raw shear stress.

Therefore, in step (b), HA/CHA suspension is preferably formed as under the influence of promoting the shear stress of laminar flow Film layer.One example of such shearing program is the thin of HA/CHA suspension of being cast or coated using slit coventry type die head coventry coating machine Film.This program, which is similar on solid substrate, coats one layer of polymeric solution.When shaping membrane, or work as roller/blade/wiper With sufficiently high speed of related movement there are when relative motion between supporting base material, roller, " doctor blade " or wiper are generated Shear stress.Quite unexpectedly with significant, such shear action enables plane HA/CHA piece along such as shearing side To arranging well.Further unexpectedly, when the liquid component in then removing HA/CHA suspension is to form at least portion When dividing the good stack layer of the HA/CHA piece of dry height arrangement, such molecules align state or preferred orientation are not destroyed. Drying layer direction in face and perpendicular between in-plane have high birefringence coefficient.

The present invention includes finding that a kind of manufacture has the simple of the film based on HA/CHA of desired six sides planar orientation Amphipathic self-assembling method.HA containing the oxygen of 5%-46% by weight is considered negatively charged amphipathic point Son, this is because the combination of its hydrophily oxygen-containing functional group and hydrophobicity basal plane.For CHA, functional group can be made to become hydrophily Or it is hydrophobic.The HA/CHA film that success prepares the planar orientation with unique six side, similar graphene does not need complicated Program.It is formed with deformational behavior on the contrary, it is synthesized by customization HA/CHA and manipulates liquid crystalline phase so that HA/CHA piece can Self assembly is realized in liquid crystalline phase.

Using atomic force microscope (AFM), Raman spectrum and FTIR characterization HA/CHA suspension to confirm its chemical state. Finally, demonstrating the presence of molten cause mesomorphic state of the HA piece (liquid crystal HA phase) in aqueous solution by crossed polarized light observation.

Two main aspects are considered to determine whether 1-D or 2-D species can form in liquid medium liquid crystalline phase: in length and breadth Enough dispersibilities or solubility in liquid medium than (ratio of length/width/diameter and thickness) and the material.HA or CHA piece is characterized by high anisotropy and monatomic or few atomic thickness (t) and usual micron-sized transverse width (w).Root According to big belly Sa case theory (Onsager's theory), when the volume fraction of high aspect ratio 2D piece is more than critical value, they can divide Liquid crystal is formed in granular media:

Vc≈ 4t/w (equation 1)

Assuming that similar graphene planes with a thickness of 0.34nm and width is 1 μm, then needed for critical size will be Vc ≈ 4t/w=4x0.34/1,000=1.36x10-3=0.136%.However, raw graphite alkene piece is inhaled due to their pi-pi accumulation Gravitation and it is not soluble in water and in common organic solvents bad dispersibility (maximum volume score, Vm, in N-Methyl pyrrolidone It (NMP) is about 0.7x10 in-5It and is about 1.5x10 in o-dichlorohenzene-5).Fortunately, the molecule knot of HA or CHA can be made Structure water and polar organic solvent (such as alcohol, n,N-Dimethylformamide (DMF) and NMP) in show good dispersibility, This is because a large amount of oxygen-containing functional groups are attached to its edge.Naturally occurring HA (for example, HA from coal) is also in humic acid It is high soluble in non-aqueous solvent, the solvent includes polyethylene glycol, ethylene glycol, propylene glycol, alcohol, sugar alcohol, polyglycereol, two Alcohol ether, solvent amine-based, the solvent based on amide, alkylene carbonates, organic acid, inorganic acid, or mixtures thereof.

Although according to theoretical prediction speculate HA/CHA critical volume fraction be likely lower than 0.2% or critical weight score it is low In 0.3%, but we have observed that the critical weight score that HA/CHA piece forms liquid crystal is significantly higher than by weight 0.4%. When the weight fraction of HA/CHA piece is in the range of 0.6%-5.0%, there are most stable of liquid crystal, this makes in wide temperature model There is high stability in enclosing.In order to study the influence that HA/CHA size forms its liquid crystal structure, the selectivity of pH auxiliary is used Sedimentation techniques prepare HA/CHA sample.It is assessed by dynamic light scattering (DLS) via three kinds of different measurement patterns and AFM The lateral dimension of HA/CHA piece.

During studying HA/CHA liquid crystal, we have a unexpected but very important discovery: HA/CHA piece exists Liquid crystalline phase in water and other solvents easily can be destroyed or be ruined with mechanical disturbance (such as mechanical mixture, shearing, turbulent flow etc.) It is bad.If by carefully removing (such as evaporation), liquid medium is without mechanically interfering liquid crystal structure, by HA/CHA piece Concentration gradually increases to more than 5% (preferably by weight from 5% to 16%), then can significantly improve the machinery of these liquid crystal Stability.We are it has further been observed, in the case where HA/CHA weight fraction is in the range of this 5%-16%, HA/CHA piece Particularly suitable for forming desired orientation coated with during forming film in casting or painting.

In terms of thermodynamics, the process that amphipathic HA/CHA is self-assembled into liquid crystalline phase is enthalpy change (Δ H) and Entropy Changes (Δ S) Interaction, as shown in equation (2): Δ GSelf assembly=Δ HSelf assembly-TΔSSelf assembly (2)

Previously to the amphipathic thermodynamic driving force for being self-assembled into liquid crystalline phase studies have shown that the contribution of entropy plays leading make With, and enthalpy change is in most cases unfavorable.The prediction of big belly Sa case theory, high aspect ratio particle can be with due to the net increase of entropy The liquid crystalline phase for being higher than critical volume fraction is formed, because the loss of orientational entropy is compensated by increased translational entropy.Specifically, The particles benefit of high aspect ratio is in formation long-range liquid crystalline phase.Another possible reason of HA/CHA aspect ratio effect may be The structural corrugations of HA/CHA piece in a solvent, because being derived from keeps the curved restoring force of piece more much weaker than along the restoring force of piece. Have been found that its aspect ratio increases, then the degree of HA/CHA corrugated form can further enhance in a solvent.This ripple Shape configuration will significantly affect the intramolecular and intermolecular interaction of the HA/CHA in suspension.

In order to realize long-range order in water-borne dispersions, it is necessary to have the good extrudings of strong long-range electrostatic repulsion HA/CHA piece.Liquid crystal structure is formed by colloidal solid and typically needs long-range repulsive force (such as electrostatic force) and short-range attractive force (such as Van der Waals force and π-π interaction) delicate balance.If long-range repulsive force is not enough to by force to overcoming short-range attractive force, glue The aggregation of body particle or the only weak formation of the lysotropic liquid crystal with minor cycle property will inevitably occur.At aqueous point of HA/CHA In granular media, long-range repulsive interactions are provided by the electric double layer that the oxygen functional group ionized is formed.Although HA/CHA piece still contains phase Attractive π-π can be effectively overcome to interact when the hydrophobic domain of big a part, but by adjusting long-range electrostatic repulsive force And Van der Waals force

The chemical composition of HA/CHA plays important work in customizing the electrostatic interaction in aqueous or organic solvent dispersion With.The increase of surface charge density will lead to increase of the electrostatic repulsion relative to the intensity of attraction.Pass through lonsdaleite plane oxygen The level of change or chemical modification can easily adjust the ratio of aromatic series and oxygen-containing domain.The decaying of HA/CHA is all-trans under emission mode Fourier transform infrared spectroscopy (FTIR-ATR) the result shows that there is the species (hydroxyl, epoxy that are oxidized on the surface HA/CHA Base and carboxyl).The oxygen functional group densities on the surface HA/CHA are detected using the thermogravimetric analysis (TGA) in nitrogen.For height The HA of oxidation has found by weight about 28% mass loss at about 250 DEG C, and is attributed to unstable oxygenated species It decomposes.When lower than 160 DEG C, the mass loss of about 16wt% is observed, the desorption of the water corresponding to Physical Absorption.The X-ray of HA It is about 1.9 that photoelectron spectroscopy (XPS) result, which shows the atomic ratio of C/O,.This shows that HA has the oxygen functional group of relative high density.This Outside, our heat or electronation time and temperature also by simply changing the HA (such as from leonardite) of heavy oxidation To prepare the HA containing the oxygen functional group compared with low-density.We have observed that it can be found that the oxygen weight fraction of liquid crystal is preferential Ground is in the range of 5%-40%, more preferably 5%-30% and most preferably 5%-20%.

Colloid interaction between HA piece can be significantly affected by ionic strength, because by reducing around HA piece Free ion concentration can effectively increase Debye-Huckel screening radius (κ -1).The electrostatic repulsion of HA liquid crystal in water can be dense with salt The increase of degree and reduce.As a result, more water are discharged from HA interlayer space, the reduction of simultaneous d spacing.Therefore, The ionic impurity in HA dispersion should be sufficiently removed, because it is the vital factor for influencing HA liquid crystal structure and being formed.

However, it was also found that introducing some a small amount of gather when making HA/CHA dispersion be subjected to casting or coating operation Close object (up to by weight 10% but preferably up to up to by weight 5% and most preferably only be up to 2%) can To help stabilizing solution crystal phase.By functional group appropriate and concentration, the GO/CFG orientation in gained film can be enhanced.This is previous Disclosure or patent document in also never taught or implied.

Then it can make to dry HA/CHA layers through heat-treated.Suitably programmed heat treatment process can be related at least two (the first constant temperature for a period of time and is then raised to second temperature and is maintained under the second temperature and hold for a heat treatment temperature Continuous another a period of time), or it is related at least two heat of initial processing temperature (the first temperature) and final HTT (being higher than the first temperature) Any other combination for the treatment of temperature (HTT).

First heat treatment temperature is being connected chemically and heat-treating for HA/CHA, and > 80 DEG C (1 can be up to, 000 DEG C but preferably up to 700 DEG C and most preferably up to 300 DEG C) at a first temperature of carry out.This is claimed herein For scheme 1:

Scheme 1 (up to 300 DEG C): (original chemical connection and thermal reduction scheme), adjacent HA/ in this temperature range Chemical combination, polymerization (edge-to-edge's merging) take place between CHA piece and is crosslinked.By multiple HA/CHA pieces with side by side and side pair The mode on side is accumulated and is chemically bound together, to form the integrated layer of the entity of similar graphene oxide.In addition, HA/ The reduction reaction of CHA layers of main experience thermal induction, causes oxygen content to reduce to about 5% or lower.The processing leads to graphene Between spacing be reduced in about 0.4nm and face thermal conductivity to increase from about 100W/mK from about 0.8-1.2nm (as former state dry) Add to 500W/mK.Even if some chemistry between HA/CHA piece can also occur even in the case where such low temperature range It connects.HA/CHA piece keeps good arrangement, but spacing keeps relatively large (0.4nm or bigger) between graphene planes.Many officials containing O It can roll into a ball and remain.

The highest of GO substance experience or final HTT are segmented into three different HTT schemes:

Scheme 2 (300 DEG C -1,500 DEG C): in this scheme being predominantly connected chemically, between adjacent HA/CHA piece Other thermal reduction and extensive chemical combination, polymerization and crosslinking occurs.HA/CHA is with graphene film (such as GO piece) (if deposited If) between can also be connected chemically.After being connected chemically, oxygen content is reduced to typically lower than 1%, leads to graphite Spacing is reduced to about 0.35nm between alkene.This means that some starting graphiteizations start at such lower temperatures, with typical case Ground needs up to 2,500 DEG C of temperature to start the graphitizable material of graphited routine (such as polyimide film of carbonization) shape At sharp contrast.This is another notable feature of HOHA film and its production method of the invention.These are connected chemically reaction and lead Thermal conductivity increases to 850-1 in cause face, and 250W/mK and/or face internal conductance rate increase to 3,500-4,500S/cm.

Scheme 3 (1,500 DEG C -2,500 DEG C): this orderly and again in graphitization scheme, occur extensive graphitization or Graphene planes merge, and structurally ordered degree is caused to significantly improve.As a result, oxygen content is reduced to typically 0.01% and stone Spacing is reduced to about 0.337nm (to depend on actual HTT and duration, realize the graphitization from 1% to about 80% between black alkene Degree).The improved degree of order also increases to > 1,300-1 by thermal conductivity in face, and 500W/mK and/or face internal conductance rate increase to 5, 000-7,000S/cm reflects.

Scheme 4 (be higher than 2,500 DEG C): in this recrystallization and integrity scheme, the big of crystal boundary and other defect occurs The movement and elimination of amount result in almost ideal monocrystalline or polycrystalline graphite alkene crystal with huge crystal grain, can compare Originate the initial grain size orders of magnitude several greatly of HA/CHA piece.Substantially eliminate oxygen content, typically 0.01%-0.1%. Spacing is reduced to about 0.3354nm (degree of graphitization is from 80% to close to 100%) between graphene, corresponding to perfect graphite monocrystalline Spacing between graphene.Absorbing to be, all graphene planes that graphene polycrystalline has are tightly packed and combine, and institute There is plane to arrange in one direction, it is perfect to be orientated.It uses by being simultaneously subjected to pyrolytic graphite in super-pressure (300Kg/ cm2) under (3,400 DEG C) of superhigh temperature generations HOPG also without generating this perfect structure being orientated.Height-oriented graphene Structure can realize such highest integrity degree under significantly lower temperature and environment (or compression of somewhat higher) pressure.By This structure obtained shows the thermal conductivity out of 1,500 up to slightly > 1,700W/mK face, and from 15,000 to 20, Face internal conductance rate within the scope of 000S/cm.

Structure derived from height-oriented HA of the invention can by at least covering first scheme (typically in the temperature Need 1-24 hour in degree range), more generally cover first two scheme (1-10 hours preferably), even more typically first three Scheme (preferably 0.5-5 hours in scheme 3), and most generally (scheme 4 continues 0.5 to 2 hour to all four schemes, can To be carried out realize highest conductivity) temperature program(me) be heat-treated HA/CHA layers and obtain.

X-ray diffractogram is obtained with the X-ray diffractometer radiated equipped with CuKcv.The displacement of diffraction maximum and broadening use The calibration of silicon powder reference substance.Use Mering equation, d002=0.3354g+0.344 (1-g) calculates degree of graphitization g by X ray picture, Wherein d002It is the graphite or graphene crystal interlayer spacing in terms of nm.Only work as d002When equal to or less than about 0.3440nm, This equation is just effective.With the d for being higher than 0.3440nm002HOHA reflect as interval base to increase spacing between graphene The presence of oxygen-containing functional group (such as similar to-OH, > O and-COOH on the plane surface of graphene).

Another knot of the degree of order of graphite film derived from HOHA of the invention and ordinary graphite crystal can be used to characterize Structure index is " inlaying the latitude of emulsion ", by the full width at half maximum (FWHM) table of the rocking curve (X-ray diffraction intensity) of (002) or (004) reflection Show.This degree of order characterization graphite or graphene crystalline size (or crystallite dimension), the amount of crystal boundary and other defect and preferably Degree of grain alignment.The almost ideal monocrystalline of graphite is characterized by having that 0.2-0.4's inlays latitude of emulsion value.Our HOHA Derivative graphite sample it is most of have inlay latitude of emulsion value (if with being not less than 2,500 DEG C within the scope of this 0.2-0.4 Heat treatment temperature (HTT) produces).However, then some values are 0.4-0.7's if HTT is between 1,500 DEG C and 2,500 DEG C In range;And if HTT between 300 DEG C and 1,500 DEG C, then some values are in the range of 0.7-1.0.

HA or graphene can be functionalised by various chemistry routes.In a preferred embodiment, gained is functionalized HA or functionalized graphite's alkene (being collectively expressed as Gn) can widely have following formula (e):

[Gn]--Rm

Wherein m is the number (typically between 1 and 5) of different functional groups type, and R is selected from SO3H、COOH、NH2、OH、R' CHOH, CHO, CN, COCl, halogen root, COSH, SH, COOR', SR', SiR'3、Si(--OR'--)yR'3-y、Si(--O--SiR '2-)OR'、R”、Li、AlR'2、Hg--X、TlZ2And Mg--X;Wherein, y is equal to or the integer less than 3, R ' are hydrogen, alkyl, virtue Base, naphthenic base or aralkyl, cyclophane base or poly- (alkyl ether), R " are fluoro-alkyl, fluorinated aryl, fluoro naphthenic base, fluoro virtue Alkyl or cyclophane base, X is halogen root, and Z is carboxylate radical or trifluoroacetic acid root.

Assuming that polymer such as epoxy resin and HA or graphene film can be combined to manufacture coating composition, then functional group- NH2It is of particular concern.For example, curing agent common for epoxy resin is diethylenetriamines (DETA), can have 2 A or more-NH2Group.-NH2One of group can be bonded on the edge or surface of graphene film, and remaining not anti- - the NH answered2Group can be used for then reacting with epoxy resin.This HA (or graphene) that is arranged in is between piece and resin additive Provide good interface cohesion.

Other useful chemical functional groups or reaction molecular can be selected from the following group, the group consisting of: amido amine, Polyamide, aliphatic amine, modified aliphatic amine, cycloaliphatic amines, aromatic amine, acid anhydrides, ketimide, diethylenetriamines (DETA), trien (TETA), tetren (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenol are hard Agent, non-brominated curing agent, non-amine hardener, with and combinations thereof.These functional groups be it is polyfunctional, have and at least two change Learn the ability that species are reacted from least two ends.Most of all, they, which are able to use one of its end, is bonded to graphene Or the edge or surface of HA, and can be in one or two other end and resin reaction during subsequent cure stage.

[Gn] described above -- RmIt can further be functionalized.Gained CFG includes the composition with following formula: [Gn] -- Am,

Wherein A be selected from OY, NHY, O=C--OY, P=C--NR'Y, O=C--SY, O=C--Y, -- CR'1--OY, N'Y or C'Y, and Y be protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotides, antigen or zymolyte, enzyme inhibitor or The appropriate functional group of the transition state analog of zymolyte is selected from R'--OH, R'--NR'2、R'SH、R'CHO、R'CN、R'X、 R'N+(R')3X-、R'SiR'3、R'Si(--OR'--)yR'3-y、R'Si(--O--SiR'2--)OR'、R'--R”、R'--N--CO、 (C2H4O--)wH、(--C3H6O--)wH、(--C2H4O)w--R'、(C3H6O)w-- R', R', and w is greater than 1 and less than 200 Integer.

HA and/or graphene film can also be functionalised to generate the composition with following formula:

[Gn]--[R'--A]m

Wherein m, R' and A are as defined above.Composition of the invention further includes adsorbing certain cyclic annular chemical combination thereon The CHA of object.These include the composition with the substance of following formula:

[Gn]--[X--Ra]m

Wherein a is zero or the number less than 10, and X is polynuclear aromatic part, more heteronuclear aromatic fractions or the more heteronuclear aromatics of metal Part, and R is as defined above.Preferred cyclic compound is plane.Preferred ring-typeization for absorption Closing object is porphyrin and phthalocyanine.The cyclic compound of absorption can be functionalised.Such composition includes the compound with following formula: [Gn]--[X--Aa]m

Wherein m, a, X and A are as defined above.

Functionalization HA of the invention or graphene can directly pass through sulfonation, electrophilic addition to the surface deoxidation GO or metallization To prepare.Graphene or HA piece can be processed before contacting with functionalized agent.This processing may include by graphene or HA piece disperses in a solvent.In some instances, then these pieces can be filtered and is dried before contact.A kind of spy Not useful type functional group is carboxylic moiety, if HA is prepared by sour intercalation route previously discussed, these carboxylic acids Part is naturally present on the surface of HA.If necessary to the carboxylic acid of additional quantity, HA piece can be made to be subjected to chlorate, nitric acid or mistake Ammonium sulfate oxidation.

Carboxylic acid functionalized graphene film is particularly useful, because they, which can be served as, is used to prepare other kinds of official The starting point of energy graphite alkene or HA piece.For example, alcohol or amide can easily be connect with acid to obtain stable ester or amide. If alcohol or amine are a part of two-or more-functional molecules, by bonded other functional groups that leave of O- or NH- as side Base.These reaction can be used as known in the art exploitation for alcohol esterification or with any method of amine amination carboxylic acid come into Row.The example of these methods can see G.W.Anderson et al., J.Amer.Chem.Soc. [American Chemical Society] 96, 1839 (1965), the document are combined herein in its entirety by reference.Amino group can be introduced directly into the following manner On graphitic fibrils: the fibrinogen of nitrification is obtained with nitric acid and sulfuric acid treatment fibrinogen, then with reducing agent such as Lian Erya Sodium sulphate electronation nitrifies form to obtain the fibrinogen of aminofunctional.

We have found that aforementioned functional groups can be attached to HA or graphene film surface or edge, in following purpose It is one or several: (a) improve the dispersion in desired liquid medium of graphene or HA;(b) enhance graphene or HA in liquid Solubility in body medium is dispersed in the graphene of sufficient amount or HA piece in the liquid, is more than to be used for liquid crystalline phase shape At critical volume fraction;(c) enhance film forming ability, allow to coat or cast the thin of originally discrete graphene or HA piece Film;(d) due to the change to flow behavior, the alignment capability of graphene or HA piece is improved;And (e) enhance graphene or HA piece It is connected chemically and is merged into the ability of bigger or broader graphene planes.

The present invention also provides a kind of rechargeable battery, the battery contains combination graphene oxide film of the invention Metal foil as anode collector and/or cathode current collector.This can be any rechargeable battery, as zinc air battery core, Nickel metal hydride battery core, sodium ion battery core, metallic sodium battery core, magnesium ion battery core, magnesium metal battery core, only list.This The battery of invention can be lithium rechargeable battery, contain integral piece graphene layer as anode collector or cathode collector Body, the lithium battery can be lithium-sulphur battery core, lithium-selenium battery core, lithium sulphur/selenium battery core, lithium-ion electric core, lithium-air battery core, lithium- Graphene battery core or lithium-carbon battery core.Another embodiment of the invention is a kind of capacitor, and the capacitor contains the present invention Collector as anode collector or cathode current collector, the capacitor is symmetrical supercapacitor, asymmetric super Capacitor battery core, hybrid super capacitor-battery battery core or lithium-ion capacitor battery core.

As example, the present invention provides a kind of rechargeable lithium-metal battery core, the lithium-metal battery core is by anode The collector at place, porous septum/electrolyte layer, contains active material of cathode (for example, being free of lithium at lithium film or foil as anode V2O5And MnO2) cathode and collector constitute.Either or both of anode collector and cathode current collector can be Collector (that is, the height-oriented film for being derived from HA or HA/ graphene mixture) based on HA of the invention.

Another example of the invention is a kind of lithium-ion capacitor (or hybrid super capacitor), the capacitor by Collector, graphite or titanate anode at anode, immersed with the porous septum of liquid or gel electrolyte, living containing cathode Property material the activated carbon of high-specific surface area (for example, with) cathode and collector constitute.Once again, the anode collector It can be the collector of the invention based on HA with either or both of cathode current collector.

Another example again of the invention is another lithium-ion capacitor or hybrid super capacitor, by anode The collector at place, graphite anode (and lithium paillon of a part as anode), immersed with liquid electrolyte porous septum, contain The cathode and collector for having active material of cathode (for example, activated carbon with high-specific surface area) are constituted.Once again, the sun Either or both of pole collector and cathode current collector can be the collector of the invention based on HA.

Still another example of the invention is a kind of lithium-graphene battery core, and the battery core is by the collector, more in anode The anode of hole nanostructure (for example, comprising the graphene film with high surface area, recharges the lithium ion of period return in battery core It can be deposited thereon, the graphene film is mixed with the lithium powder particle of surface-stable;Or has and be attached in nanostructure Lithium paillon), immersed with liquid electrolyte porous septum, comprising based on graphene active material of cathode (for example, have height Specific surface area with during battery core is discharged capture lithium ion graphene, graphene oxide or graphene fluoride piece) yin Pole and cathode current collector are constituted.Once again, either or both of the anode collector and cathode current collector can be this The collector based on HA of invention.

Example 1: humic acid and reduction humic acid from leonardite

It, can be with very high yield (75% by the way that leonardite to be dispersed in alkaline aqueous solution (pH 10) In range) extracted humic acid from leonardite.Subsequent souring soln leads to humic acid powder precipitation.In an experiment, in magnetic force Under stirring, contain 1M KOH (or NH with 300ml4OH) the leonardite of the 3g of deionized water dissolving twice of solution.By pH value tune It saves to 10.Then filtering solution is to remove any bulky grain or any residual impurity.

By gained humic acid dispersion (containing individual HA or in which there are the HA of graphene oxide sheet), (GO is retouched following Prepared in the example 3 stated) be coated on Cu foil or Ti foil surface, form the Cu foil or Ti paper tinsel film of a series of combination HA, for Heat treatment afterwards is to obtain A type collector.

In order to compare, similar film is cast on glass surface, and is then removed before subsequent heat treatment, with Prepare Type B collector.

Example 2: humic acid is prepared by coal and combines the metal foil collector of HA

In typical program, 300mg coal is suspended in the concentrated sulfuric acid (60ml) and nitric acid (20ml), and then cup is super Sonication 2h.Then reaction is stirred in 100 DEG C or 120 DEG C of oil bath and is heated for 24 hours.Solution is cooled to room temperature and is fallen Enter in the beaker containing 100ml ice, followed by addition NaOH (3M) until pH value reaches 7 the step of.

In an experiment, then neutral blends are filtered by 0.45-mm polytetrafluoroethylene film, and by filtrate It dialyses 5 days in 1,000Da bag filter.For biggish humic acid piece, using cross flow one ultrafiltration can will foreshorten to the time 1 to 2h.After purifying, using rotary evaporation concentrate solution to obtain solid humic acid piece.By these individual humic acid pieces and its with The mixture of graphene film is redispersed in solvent (respectively ethylene glycol and alcohol) to obtain several dispersion samples, for After cast or be coated on Al foil and stainless steel foil.It is prepared for both A type and Type B collector.

Example 3: graphene oxide (GO) piece is prepared by natural graphite powder

Use the natural graphite from Ai Siborui carbon company (Ashbury Carbons) as starting material.GO is What the Hummers method by following well-known modification obtained, the method is related to two oxidation stages.In typical journey In sequence, oxidation is realized under the following conditions for the first time: 1100mg graphite is placed in 1000mL kieldahl flask.Then, in flask The middle K that 20g is added2S2O8, 20g P2O5With the dense H of 400mL2SO4Aqueous solution (96%).It is small that mixture is heated to 6 under reflux When and then at room temperature undisturbed stand 20 hours.Graphite oxide is filtered to and is used a large amount of distilled water flushings, until reaching PH value > 4.0.Wet cake shape material is recycled at the end of aoxidizing first time.

For second of oxidation process, the wet cake collected before is placed in containing the dense H of 69mL2SO4The length of aqueous solution (96%) In neck flask.It keeps the flask in ice bath, while being slowly added to 9g KMnO4.Pay attention to avoiding overheating.Gained mixture is existed It is stirred at 35 DEG C 2 hours (color sample becomes bottle green), 140mL water is then added.After 15 minutes, by the way that 420mL water is added With 15mL 30wt%H2O2Aqueous solution stop reacting.Become glassy yellow in the color of this stage sample.In order to remove gold Belong to ion, mixture is filtered and the HCL aqueous solution of 1:10 is used to rinse.The material of collection is mildly centrifuged at 2700g and is used in combination Deionized water is rinsed.Wet cake of the final products containing 1.4wt%GO (estimating from dry extracts).Then, by slightly surpassing Diluted wet cake material obtains the liquid dispersion of GO platelet in deionized water for sonication.

Individually on the basis of, preparation containing different GO ratios (1%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, the water slurry of the mixture of 80%, 90% and GO 99%) and humic acid and slit die head painting is carried out coated with production The film of raw various compositions.

Example 4: the preparation of the alignment films containing humic acid and raw graphite alkene piece (0% oxygen) mixture

In typical program, about 20 μm are milled to by 5 grams or smaller size of graphite flake is scattered in 1,000mL and goes Ionized water (containing by weight 0.1% dispersing agent, from E.I.Du Pont Company (DuPont)FSO to be hanged in) Supernatant liquid.Extruding, separation and the ruler of graphene film are used for using the ultrasound energy level (Branson S450 ultrasonic generator) of 85W Very little reduction continues 15 minutes to 2 hours periods.Gained graphene film is from not oxidized and be anaerobic and opposite do not have Defective raw graphite alkene.Raw graphite alkene is substantially free of any non-carbon element.

Suspension after ultrasonic treatment contains the raw graphite alkene piece being dispersed in water and is dissolved in surface-active therein Agent.Then humic acid is added in suspension, and gained mixture suspension is further ultrasonically treated 10 minutes, to promote Evenly dispersed and mixing.Then it applies the dispersion on Cu and Ti foil, and in order to compare, is coated before the heat treatment Onto glass and PET film.

Example 5: height-oriented graphite film is prepared from the mixture of fluorinated graphene piece and humic acid

We have been several methods to produce GF, but only describe a kind of method herein as example. In typical program, highly bulked graphite (HEG) is by intercalation compound С2F·xClF3Preparation.HEG is steamed by chlorine trifluoride Gas is further fluorinated to generate fluorinated highly bulked graphite (FHEG).The teflon reactor pre-cooled is filled with 20- The ClF that 30mL liquid pre-cools3, reactor is closed and is cooled to liquid nitrogen temperature.Then, the HEG no more than 1g is put into In container, the container, which has, is used for ClF3The hole that gas enters reactor and is located in reactor.Foring in 7 days has Approximate expression C2The cream-coloured product of ash of F.

Then, a small amount of FHEG (about 0.5mg) is mixed with 20-30mL organic solvent (respectively methanol and ethyl alcohol) and makes it It is subjected to ultrasonic treatment (280W) and continues 30 minutes, result in uniform faint yellow dispersion.Then with various HA and GF ratios Humic acid is added in these dispersions.Then dispersion is made by Cu using comma formula coating (comma coating) The film of foil support.Then different degrees of heat treatment is carried out to height-oriented HA film, to obtain highly conductive property graphite film.

Example 6: the preparation of the HOHA film containing nitridation graphene film and humic acid

By the urea fine gtinding of graphene oxide (GO) different proportion synthesized in example 3, and by the mixture of granulation 30s is heated in microwave reactor (900W).Product is washed with deionized for several times and is dried in vacuo.In this approach, oxygen Graphite alkene is restored simultaneously and doped with nitrogen.It is that 1:0.5,1:1 and 1:2 obtain product, and this with graphene/urea mass ratio The nitrogen content of a little samples is respectively such as to pass through 14.7wt.%, 18.2wt.% and 17.5wt.% of determination of elemental analysis.These nitrogen Graphite alkene piece keeps can be dispersed in water.The HA of various amounts with 20.5% to 45% oxygen content is added to suspension In.

Then to form wet film, then gained nitridation graphene-HA dispersion liquid suspension is coated in plastic film substrate The wet film is dried and is removed from plastic foil, and makes it from 80 DEG C to 2,900 DEG C of different heat treatment temperature It is lower through heat-treated, with obtain height-oriented humic acid (HOHA) film (if final HTT < 1,500 DEG C) or high-sequential and Conductive graphite film (if under 1,500 DEG C or higher temperature).Then these films are integrated to Ti using resin binder With the surface Cu, to prepare Type B collector.In addition, for comparison purposes, also by a certain amount of nitridation graphene-HA dispersion Suspension is coated on Ti and Cu foil surface to form wet film, is then dried and is heat-treated up to 1 respectively, 500 DEG C and 1,250℃。

Example 7: the highly conductive property film for being prepared nematic liquid crystal by humic acid piece and being generated by humic acid piece

The dispersion of HA piece is prepared into humic acid water-borne dispersions in deionized water by being mildly ultrasonically treated.Pass through dialysis Any acid or ionic impurity in dispersion is removed, this is the step most important for Formation of liquid crystals.

Enough for a long time low concentration dispersion (the typically 0.05wt.%- of (usually more than 2 weeks) by immobilization It 0.6wt.%) is separated into two-phase on a macro scale.Although be mutually at the top of low-density it is optically isotropic, high density bottom mutually exists Optical birefringence outstanding is shown between two crossed nicols.It is observed in the phase of bottom and brushes the allusion quotation formed with bright by secretly brushing Type nematic schlieren texture.This is two-phase behavior, and wherein isotropic phase and nematic phase coexist.Due to the polydispersity of HA molecule Greatly, therefore the compositing range of two-phase is comparatively wide.It is noted that ionic strength and pH value significantly affect the stability of HA liquid crystal. The electrostatic repulsion of surface functional group such as carboxylate radical from dissociation plays a crucial role in the stability of HA liquid crystal.Cause This, reduces the condensation that repulsive interactions increase HA piece by increasing ionic strength or reducing pH value.

It is observed that essentially all HA piece forms liquid crystalline phase, and leads to when HA piece accounts for 1.1% weight fraction Liquid crystal can be kept for the range that the concentration of HA progressively increases to from 6% to 16% by crossing.The humic acid dispersion of preparation is for meat Eye shows the appearance of non-uniform chocolate emulsus.This milky appearance may be takeed for the aggregation or heavy of graphene oxide It forms sediment, but actually it is nematic crystal.

By HA suspension being distributed in slurry coating machine and is coated on polyethylene terephthalate (PET) film And liquid medium is removed from coating film, we obtain the films of dry HA.Before the heat treatment, by dry film from PET film removing is to become free-standing films.In addition, also HA suspension is coated on Cu foil or the surface Ti, and then dry.So Each film (both the films supported from the PET free-standing films removed and Ti or Cu) is set to be subjected to different heat treatment afterwards, at the heat Reason continues 1-10 hours at a first temperature of typically comprising 80 DEG C to 300 DEG C, and at 1,500 DEG C -2, the second of 850 DEG C At a temperature of continue 0.5-5 hour be connected chemically and thermal reduction handle.The film of the film of Cu support and Ti support is heat-treated respectively Up to only 1,250 DEG C and 1,500 DEG C.With these heat treatments, also under compressive stress, HOHA film is transformed into highly conductive property Graphite film (HOGF).

Have studied the internal structure (crystal of several HA layers dry (HOHA film) and HOGF in the different phase of heat treatment Structure and orientation).HOHA layers of drying before being heat-treated, the HOHA film and gained that 5 hours are heat-treated at 150 DEG C The X-ray diffraction curve of HOGF.Dry HOHA layers of the peak at about 2 θ=12 ° corresponds approximately to the graphene of 0.75nm Between spacing (d002).By some heat treatments at 150 DEG C, desciccator diaphragm shows the hump to be formed centered on 22 °, shows The process for reducing interplanar spacing is had begun, shows to be connected chemically the beginning with order process.Pass through 2,500 DEG C of heat treatment Constant temperature 1 hour, the d of film (being not bonded to metal foil)002Spacing has been reduced to about 0.336, close to graphite monocrystalline 0.3354nm。

Continue 1 hour by 2,750 DEG C of heat treatment temperature, is not bonded to the d of the film of metal surface002Spacing has reduced It is identical with graphite monocrystalline to about 0.3354nm.In addition, having the second high-intensitive diffraction maximum corresponding to from (004) Occur at 2 θ=55 ° of the X-ray diffraction of plane.(004) peak intensity on same diffraction curve is strong relative to (002) Degree or I (004)/I (002) ratio, are the crystal perfection degree of graphene planes and the good instruction of preferred orientation degree.This field It is well known that (004) peak is to be not present for heat treated all Conventional graphite materials at a temperature of lower than 2,800 DEG C Or relatively weak, wherein I (004)/I (002) ratio < 0.1.Graphite material (the example being heat-treated at 3,000 DEG C -3,250 DEG C Such as height-oriented pyrolytic graphite, HOPG) I (004)/I (002) ratio in the range of 0.2-0.5.In contrast, with 2, 750 DEG C of final HTT continues to show within one hour 0.77 I (004)/I (002) ratio from the HOGF of the film preparation based on HA liquid crystal Rate and 0.21 inlays latitude of emulsion value, shows the actually perfect graphene monocrystalline with abnormal high preferred orientation degree.

The full width at half maximum (FWHM) that " inlaying the latitude of emulsion " value is reflected from (002) in X-ray diffraction intensity curve obtains.This degree of order Index characterization graphite or graphene crystalline size (or crystallite dimension), the amount of crystal boundary and other defect and preferred crystal grain The degree of orientation.The almost ideal monocrystalline of graphite is characterized by having that 0.2-0.4's inlays latitude of emulsion value.It is not less than 2 when using, 500 DEG C of final heat treatment temperature is come when producing, the most of of HOGF derived from our HA have within the scope of this 0.2-0.4 Inlay latitude of emulsion value.

It is noted that the I (004) for the whole dozens of soft graphite foil green compacts studied/I (002) ratio is all Be < < 0.05, in most cases not actually exist.Even if after being heat-treated 2 hours at 000 DEG C, using vacuum aided 3 Filter method preparation all graphene paper/film samples I (004)/I (002) ratio < 0.1.These observe results into one Step confirm following viewpoint: HOHA film of the invention be with any pyrolytic graphite (PG), soft graphite (FG) and ordinary graphite alkene/ GO/RGO piece/platelet (NGP) paper/film/film fundamentally different a new class of and unique material.

Pass through the liquid-derived HOGF of two kinds of HA liquid crystal suspensions being heat-treated under the different temperatures in wide temperature range Distance values are summarized in Fig. 5 (A) between the graphene of sample.Corresponding oxygen content value is shown in Fig. 5 (B).In order to show graphite Correlation between alkene between spacing and oxygen content repaints the data in Fig. 5 (A) and Fig. 5 (B) in Fig. 5 (C).To Fig. 5 (A) to examining for Fig. 5 (C) shows that there are four (100 DEG C -300 DEG C of HTT range;300℃-1,500℃;1,500℃- 2,000℃;With > 2,000 DEG C), generate four corresponding spacing ranges between oxygen content range and graphene.HA liquid crystal derived The thermal conductivity of HOGF sample and corresponding soft graphite (FG) foil sample is (also as identical final heat treatment temperature range Function and draw) be summarised in Fig. 5 (D).All these samples all have comparable thickness value.

It is important to note that, it is more next lower than 0.4nm to be enough spacing between making mean level of the sea down to 500 DEG C of heat treatment temperatures The spacing between the mean level of the sea of natural graphite or graphite monocrystalline.The pleasant place of this method is following viewpoint: the HA liquid crystal is outstanding Supernatant liquid strategy allows us to the recombination of plane HA piece, reorientation and chemistry being merged into unified structure, wherein all classes Like the plane at this moment larger (length and width of the lonsdaleite plane in noticeably greater than original HA molecule on lateral dimension of graphene Degree) and be substantially parallel to each other.It has been that 300-400W/mK (HTT is 500 DEG C) and > 623W/mk (only come that this, which has been generated, From the thermal conductivity of HA) or > 900W/mk (mixture from HA+GO) (HTT is 700 DEG C), this is than corresponding soft graphite foil It is big more than 3 to 4 times to be worth (200W/mK).In addition, the tensile strength of HOGF sample can reach 90-125MPa (Fig. 7 (A)).

In HTT down in the case where 1 000 DEG C, the height-oriented HA film of gained shows respectively 756W/mK (from single Only HA) and 1,105W/mK (come from HA-GO mixture) thermal conductivity.This with observed with identical heat treatment temperature it is soft Property graphite foil 268W/mK formed sharp contrast.In fact, no matter HTT how high (for example, even as high as 2,800 DEG C), it is flexible Graphite foil only shows the thermal conductivity lower than 600W/mK.At 2,800 DEG C of HTT, HOGF layer of the invention is derived from HA and GO The layer of mixture provide the thermal conductivity (Fig. 4 (A) and Fig. 5 (D)) of 1,745W/mK.It is further noted that such as Fig. 4 (A) Shown, the heat conductivity value of graphite film derived from HA/GO mixture is consistently higher than the corresponding graphite film derived from graphene oxide Heat conductivity value.It is further discussed this unexpected effect in example 8.

Scanning electron microscope (SEM), the transmission electron microscope (TEM) of the lattice imaging of graphene layer are also carried out Figure and selective electron diffraction (SAD), light field (BF) and dark field (DF) image are to characterize the structure of integral piece grapheme material. In order to measure the section view of film, sample is buried in the polymer matrix, is sliced using ultramicrotome, and with Ar plasma Body etching.

Carefully studying for Fig. 2, Fig. 3 (A) and Fig. 3 (B) shows that similar graphene layer is substantially put down each other in HOGF with comparing Row orientation;But for soft graphite foil and graphene oxide paper, situation is not in this way.Two can know in highly conductive property graphite film Inclination angle between other layer is usually less than 10 degree and in most cases less than 5 degree.In contrast, exist such as in soft graphite Folding graphite flake, kink and misorientation so that many in angle between two graphite flakes is greater than 10 this more Degree, some up to 45 degree (Fig. 2).Although misorientation (Fig. 3 between graphene platelet without so bad, in NGP paper It (B)) is also that there are many gaps between high and platelet.HOGF entity is substantially gapless.

Fig. 4 (A) respectively illustrates film derived from the HA/GO drawn as the function of final HTT, film, HA derived from GO The heat conductivity value of HOGF and soft graphite derived from suspension (FG) foil.These data have clearly demonstrated of the invention Superiority of the HOGF structure derived from HA/GO under given heat treatment temperature in terms of achievable thermal conductivity.

1) at a temperature of comparable final heat treatment, the liquid-derived HOGF of HA/GO liquid crystal suspension in terms of thermal conductivity seemingly The HOGF gel derived better than GO.Even if after heat-treating and being graphitized again, the heavy oxidation of graphene film in GO gel It may cause the high defects count on graphene surface.However, the presence of HA molecule seems to help to repair defect or bridge joint Gap between GO piece.

2) although the height-oriented film derived from individual HA shows the heat slightly below derived from those of individual GO Conductivity value, but the HA as material is abundant in nature and it generates HA without using undesirable chemicals. HA an order of magnitude cheaper than natural graphite (raw material of GO), and the 2-4 order of magnitude cheaper than GO.

3) in order to compare, we also obtain conventional height-oriented pyrolytic graphite from polyimides (PI) carbonization approach (HOPG) sample.Polyimide film continues 1 hour at 500 DEG C in an inert atmosphere, continue 3 hours at 1,000 DEG C and Continue to be carbonized for 12 hours at 1,500 DEG C.Then the PI film of carbonization is being pressed at a temperature in the range of 2,500 DEG C -3,000 DEG C Graphitization continues 1 to 5 hour under contracting power, to form conventional HOPG structure.

Fig. 4 (B) shows HOGF, HA derived from the HA/GO suspension drawn as the function of final heat treatment temperature The heat conductivity value of HOPG derived from HOGF and polyimides derived from suspension.These data are shown, it is assumed that identical HTT is held The heat treatment time of continuous equal length, compared with HOGF derived from HA/GO, by using polyimides (PI) the approach institute of carbonization The conventional H OPG of generation shows consistently lower thermal conductivity.For example, the graphitization processing at 2,000 DEG C of the HOPG from PI The thermal conductivity of 820W/mK is shown after continuing 1 hour.Under identical final graphitization temperature, HOGF derived from HA/GO shows The heat conductivity value of 1,586W/mK out.It is noted that PI also several orders of magnitude more expensive than HA, and if PI production be related to using Dry kind of environmentally undesirable organic solvent.

4) these observation results are proved to produce HOGF using HA/GO or HA suspension method relative to the life of conventional PG method Produce the clear and significant advantage of orientation graphite crystal.In fact, no matter HOPG graphitization time how long, thermal conductivity is always lower than The thermal conductivity of the HOGF of HA/GO liquid crystal derived.It has also been unexpectedly found that humic acid molecule can mutual chemical connection to be formed Strong and highly conductive property graphite film.It is obvious that in chemical composition, crystal and defect sturcture, crystal orientation, form, production technology In terms of characteristic, height-oriented HA film (including height-oriented HA/GO film) and subsequent heat treatment pattern are fundamentally different In and be clearly distinguishable from soft graphite (FG) foil, graphene/GO/RGO paper/film and pyrolytic graphite (PG).

5) data in Fig. 4 (C) further support above-mentioned conclusion, show in the entire scope of the final HTT studied, The conductivity value of HOGF derived from HOGF and HA suspension derived from HA/GO suspension is much better than the conductivity value of FG paillon.

Example 8: graphene is added to the characteristic of the height-oriented graphite film based on HA and graphite film as derived from it It influences

Graphene oxide (GO) piece of various amounts is added to obtain mixture suspension in HA suspension, wherein HA and GO piece disperses in liquid medium.Then the HOGF sample of various GO ratios is produced according to program identical with above description.This The thermal conductivity data of a little samples is summarised in Fig. 6, shows that the heat conductivity value of the HOGF produced by HA-GO mixture is higher than by independent One-component production HOGF film heat conductivity value.

Further unexpectedly, when both HA piece and GO piece coexist in proper proportions, it can be observed that collaboration effect It answers.Seem that HA can help GO piece (being known to be height defect) to repair from them originally defective structure.It is also possible to , size significantly less than GO piece/molecule HA molecule can fill the gap between GO molecule and react with it with bridge between Gap.The two factors may cause conductibility and significantly improve.

Example 9: the tensile strength of HOHA film derived from various graphene oxides

By being prepared using comparable final heat treatment temperature derived from a series of HA/GO dispersions to all material HOGF film derived from HOGF derived from HOGF, GO dispersion and HA.Determine that the stretching of these materials is special using universal testing machine Property.Fig. 7 (A) and Fig. 7 (B) respectively illustrate the tensile strength and drawing of these the various samples prepared in heat-treatment temperature range Stretch modulus.In order to compare, some tensile strength datas of RGO paper and soft graphite foil are also summarised in Fig. 7 (A).

These data are it has been proved that the tensile strength of the derivative piece of graphite foil is slightly increased with final heat treatment temperature (from 14 To 29MPa), and when final heat treatment temperature from GO paper when increasing to 2,800 DEG C for 700 DEG C (GO paper through compression/heated Piece) tensile strength increase to 52Mpa from 23Mpa.In contrast, in identical heat-treatment temperature range, derived from HA The tensile strength of HOGF is increased significantly to 93MPa from 28MPa.Most significantly, the stretching of HOGF derived from HA/GO suspension is strong Degree is increased significantly to 126MPa from 32Mpa.This is the result is that quite surprising and further reflect following viewpoint: HA/GO and HA dispersion contains the chemically active HA/ for capableing of mutual chemical connection and the height-oriented/arrangement merged during heating treatment GO and HA piece/molecule, and the graphite flake in the graphene platelet and FG foil in routine GO paper is substantially dead platelet.It is based on The height-oriented film of HA or HA/GO and inherently a kind of new material of the graphite film then produced.

As reference, obtained and simply spraying to HA- solvent solution on glass surface and by solvent seasoning Film does not have any intensity (it is such fragile so that you with finger touch membrane simply by that can make film broken).> After being heat-treated at a temperature of 100 DEG C, which becomes fragment (being broken into a large amount of piece).In contrast, height-oriented HA film (its In all HA molecules or piece be height-oriented and be packed together), after being heat-treated 1 hour at 150 DEG C, become have it is good Structural intergrity has the > film of the tensile strength of 24MPa.

Example 10: the novel influence that metal foil is connected chemically the thermal induction of humic acid molecule

Shown in fig. 8 is the heat conductivity value of film height-oriented derived from three kinds of HA.The first be by heat treatment from What the HA film of glass surface removing obtained.It is applied on the surface Ti for second, and the film is integrated to during heating treatment The surface Ti.The third is applied on Cu foil surface, and is integrated to Cu foil surface during heating treatment.In identical final heat Under treatment temperature, with before the heat treatment from those of film of PET film sur-face peeling compared with, the HA film of metal foil support is shown Significant higher heat conductivity value.Cu and Ti foil seems the thermal induction between the humic acid molecule that can be in close contact to Cu or Ti It is connected chemically or merges and certain catalytic action is provided.This is really unexpected.It is even more surprising that discovery conductivity Difference is very big.In addition, the HA film after being heat-treated at 1,250 DEG C shows the heat of Isosorbide-5-Nitrae 32W/mK when being supported on Cu foil Conductance.After being heat-treated identical time span at 2,500 DEG C, film derived from HA realizes identical value, without by Cu or Ti The benefit of catalysis.

Example 11: contain the Li-S battery core of the metal foil collector in conjunction with humic acid at anode and cathode

Three kinds of (3) Li-S battery cores are prepared and test, each is with lithium foil as active material of positive electrode, sulphur/expansion stone 1M LiN (CF of the black composite material (75/25 weight ratio) as active material of cathode, in DOL3SO2)2As electrolyte, with And Celgard 2400 is used as diaphragm.The first battery core (the baseline battery core for comparing) contains 10 μ m-thick Cu foils as anode collection Fluid and 20 μ m-thick Al foils are as cathode current collector.Second of battery core (another baseline battery core for comparing) has 10 μ m-thicks GO- resin layer is as anode collector and the Al paillon of 14 μm of RGO coating as cathode current collector.The third battery core has this The Cu foil (12 μ m-thick in total) of the combination HA of invention is as anode collector and the Al paillon of 20 μ m-thick HA coating as cathode collection Fluid.

It periodically measures charge storage capacity and the function as recurring number is recorded.Ratio mentioned by this paper is put Capacitance is that the total electrical charge/unit mass composite cathode being inserted into cathode during electric discharge (calculates active material of cathode, conduction The weight of additive or supporter and adhesive, but collector forecloses).The specific energy that presents in this section and compare function Rate value is based on total battery core weight (including anode and cathode, diaphragm and electrolyte, collector and packaging material).Using saturating It penetrates both electron microscope (TEM) and scanning electron microscope (SEM) and observes selected sample in the recharge of desired number With the form or microstructure change after recharge cycle.

Fig. 9 (A) shows the discharge capacity value of these three battery cores, respectively as the function of charge/discharge cycle number.In order to Convenient for comparing, each battery core is designed to have the initial battery core capacity of 100mAh.Obviously, with the sheet at anode and cathode two The Li-S battery core that the collector of the combination HA of invention is characterized shows most stable of circulation behavior, experienced after 50 circulations 6% capacitance loss.The battery core of the Al collector of Cu and GO coating containing the coating of GO/ resin is subject to after 50 circulations 23% capacity attenuation.Battery core containing Cu foil anode collector and Al foil cathode current collector is subject to 26% appearance after 50 circulations Amount decaying.Check that the Al foil shown in the electrode of all prior arts all suffers from serious corrosion and asks after the circulation of these battery cores Topic.In contrast, the Al collector of combination of the invention oxidation humic acid keeps complete.

Fig. 9 (B) shows the Ragone curve graph of three kinds of battery cores (gravimetric power density is to gravimetric energy density).Have Interest is it is noted that the graphene at anode/resin coating collector with the prior art (is wherein that GO is applied at cathode The Al foil covered) it is compared with Cu/Al collector, the metal foil collector of our combination HA unexpectedly imparts Li-S electricity Both the higher energy density of core and higher power density.In view of Cu foil is with higher than the conductivity of graphene film and HA film More than the conductivity of an order of magnitude, this is quite unexpected.

Example 12: contain the magnesium ion battery core of the collector of HA realization at anode and cathode

In order to prepare active material of cathode (manganous silicate magnesium, Mg1.03Mn0.97SiO4), in a vacuum at 150 DEG C after dry 3h Use SILVER REAGENT KCl (fusing point=780 DEG C) as fluxing agent.Starting material is magnesia (MgO), manganese carbonate (II) (MnCO3) With silica (SiO2, 15-20nm) and powder.The stoichiometric amount of precursor compound is rubbed with the Mg:Mn:Si of 1.03:0.97:1 You are than control.By mixture (fluxing agent/reactant molar ratio=4) by pestle hand-ground 10 minutes in mortar, and It is subsequently poured into corundum crucible.Then, will at mixture of powders in a vacuum 120 DEG C dry 5h so that water content in mixture It minimizes.Then, mixture is immediately transferred in tube furnace and in reducing atmosphere (Ar+5wt%H2) at 350 DEG C 2h is heated to remove carbonate group.After this, 6h is fired finally with the rate of 2 DEG C/min at different temperatures, then certainly So it is cooled to room temperature.Finally, by product (manganous silicate magnesium, Mg1.03Mn0.97SiO4) be washed with deionized and appointed three times with dissolution What remaining salt, by centrifuge separation, and dry 2h at 100 DEG C in a vacuum.

Prepare electrode (anode or cathode) typically via following manner: by the electrode active material of 85wt% (for example, Mg1.03Mn0.97SiO4(PVDF, 5wt% are solid for particle, 7wt% acetylene black (Super-P) and 8wt% polyvinylidene binder Body content is dissolved in n-methyl-2-pyrrolidone (NMP)) it is mixed to form pulp-like mixture.It is pre- slurry to be coated in After on the collector of phase, before pressing by 2h dry at the electrode obtained in a vacuum 120 DEG C to remove solvent.Having studied has Three kinds of battery cores of different collectors: the first battery core has Cu foil and the combination of the combination HA respectively as anode and cathode collector The Al foil of HA;There is second battery core (battery core of the prior art) the GO/ resin respectively as anode and cathode collector to coat Cu foil and the Al foil of GO coating (not having pre-etched);Third battery core (battery core of the prior art) has Cu foil anode collector and Al Foil cathode current collector.

Then, the electrode is cut into disk (diameter=12mm), is used as cathode.Magnesium tinsel thin slice is attached to anode collector On surface, and a piece of porous septum (for example, 2400 film of Celgard) is stacked on the top of the magnesium foil in turn.It will apply The a piece of cathode disc overlayed on cathode current collector is used as cathode and is stacked on membrane layer to form CR2032 coin shape battery core. Used electrolyte is the 1M Mg (AlCl in THF2EtBu)2.Battery core is assembled in the glove box of argon gas filling and carries out.Make CV measurement is carried out with the sweep speed of 1mV/s with CHI-6 electrochemical workstation.Also use Arbin and/or LAND electrochemical operation Stand by under the current density from 50mA/g to 10A/g (for some battery cores, up to 100A/g) carry out constant current charge/ Discharge cycles evaluate the chemical property of the battery core.

Figure 10 shows the battery core specific discharge capacity value of three kinds of battery cores, individually as charge/discharge cycle number Function.Obviously, the Mg ion battery core characterized by collector of the invention at anode and cathode two is shown most stable of Circulation behavior experienced 2.5% capacitance loss after 25 circulations.The Al of Cu foil containing the coating of GO/ resin and GO coating The battery core of foil collector is subject to 17% capacity attenuation after 25 circulations.Contain Cu foil anode collector and Al foil cathode collector The battery core of body is subject to 30% capacity attenuation after 25 circulations.It is checked after the circulation of the battery core and shows the coating of GO/ resin Cu foil and the Al foil collector of GO coating become to be swollen and show some layerings with cathode layer, and Al foil is by serious Etching problem.In contrast, the metal foil collector of combination HA of the invention keeps complete.

Example 13: the chemistry and mechanical compatibility of the different collectors of the battery or supercapacitor for heterogeneous expectations are surveyed Examination

As proved in above example 11 and 12, length of the collector of battery or supercapacitor relative to electrolyte Phase stability is to be primarily upon.In order to understand the chemical stability of different collectors, groundwork has been carried out: by collector exposure In several representative electrolyte.After extended period (for example, 30 days), the collector is moved from electrolyte solution It is observed out and using optics and scanning electron microscope (SEM).As a result it is summarized in the following table 3, these results are consistently Show the liquid electrolytic of the metal foil collector and all kinds for being usually used in battery and supercapacitor of combination HA of the invention Matter highly compatible.Material of the invention is any chemical erosion of tolerance.The collector of these HA protection is relative to Li/Li+ 0-5.5 volt voltage range in be substantially electrochemicaUy inert, be suitable for and substantially any battery/capacitor electrolyte It is used together.

It is noted that each collector is necessarily connected on tab, the tab is connected to external circuit electric wire in turn. The collector must be it is mechanical compatible with tab, be easy to or easily fixed or be bonded thereto.We have found that CVD graphene film cannot be exactly mechanically secured on tab in the case where not easily damaged or fracture.Even in Adhesive, the cvd film are also to be easily broken off during the program for being connected to tab or battery battery core packaging.

Table 3: collector-electrolyte phase capacitive test result.

In short, we have successfully developed a kind of absolutely new, novel, unexpected and visibly different height Conductive of material: it is incorporated in film derived from the humic acid in one or more metal foil surfaces.The chemical group of such new material At, structure (crystal perfection, crystallite dimension, defects count etc.), crystal orientation, form, production technology and characteristic fundamentally not Be same as and be clearly distinguishable from pyrolytic graphite derived from freestanding or coating soft graphite foil on metal foil, polymer, PG derived from CVD (including HOPG) and catalysis CVD graphene film.Thermal conductivity, the conductance shown by material of the invention Rate, scratch resistance, surface hardness and tensile strength are than the flexible graphite platelet of the prior art, discrete graphene/GO/RGO platelet Paper or other graphite films are in the cards wants much higher.Membrane structure derived from these HA has excellent conductivity, thermal conductivity Rate, mechanical strength, surface scratch resistance, hardness and the optimal combination without peeling tendency.

Claims (53)

1. a kind of for combining the metal foil collector of humic acid, the collector packet used in the battery or supercapacitor It includes:
(a) thin metal foil, the thin metal foil have the thickness and two opposite but substantially parallel main tables from 1 μm to 30 μm Face;And
(b) film of the mixture of at least one humic acid (HA) or HA and graphene film or highly conductive property as derived from it Graphite film, wherein the film or the graphite film of HA the or HA/ graphene mixture are chemically bonded to the institute of the metal foil State at least one of two opposite major surfaces;
Wherein when independent measurement in the case where no thin metal foil, the film of the HA or HA/ graphene mixture Or the graphite film have thickness from 5nm to 10 μm, by weight from 0.01% to 10% oxygen content, from 1.3 to 2.2g/ cm3Phsyical density, be substantially parallel to each other and be parallel to the lonsdaleite plane of main surface orientation, lonsdaleite plane it Between 0.335 to 0.50nm interplanar spacing, the thermal conductivity greater than 250W/mK and the conductivity greater than 800S/cm.
2. collector as described in claim 1, wherein each of described two opposite major surfaces and the humic acid or The film of HA/ graphene mixture or graphite film chemical bonding.
3. collector as described in claim 1, wherein the film of the HA or HA/ graphene or the graphite film chemistry knot At least one of described two opposite major surfaces of the metal foil are closed without the use of adhesive or adhesive.
4. collector as described in claim 1, wherein the film of the HA or HA/ graphene or the graphite film are used and glued Mixture or adhesive are integrated at least one of described two opposite major surfaces of the metal foil.
5. collector as claimed in claim 4, wherein described adhesive or adhesive are selected from inherently conductive polymerization Object, pitch, amorphous carbon or carbide resin conductive material.
6. collector as described in claim 1, wherein thickness of the thin metal foil with from 4 to 12 μm and the corruption The film for growing acid or HA/ graphene mixture has thickness from 20nm to 2 μm.
7. collector as described in claim 1, wherein at least one described main surface does not contain passive metal oxidation on it Nitride layer.
8. collector as described in claim 1, wherein the metal foil is selected from Cu, Ti, Ni, stainless steel, Al foil or its group It closes.
9. collector as described in claim 1, wherein the film or graphite film have by weight from 1% to 5% oxygen Content.
10. collector as described in claim 1, wherein the film or graphite film have oxygen content less than 1%, are less than The interplanar spacing of 0.345nm and conductivity not less than 3,000S/cm.
11. collector as described in claim 1, wherein the film or graphite film have less than 0.1% oxygen content, small In the interplanar spacing of 0.337nm and not less than the conductivity of 5,000S/cm.
12. collector as described in claim 1, wherein the film or graphite film have oxygen content no more than 0.05%, Interplanar spacing less than 0.336nm inlays latitude of emulsion value and the conductivity not less than 8,000S/cm no more than 0.7.
13. collector as described in claim 1, wherein the film or graphite film are between the interplanar less than 0.336nm Away from, no more than 0.4 inlay latitude of emulsion value and greater than the conductivity of 10,000S/cm.
14. collector as described in claim 1, wherein the film or graphite film show the interplanar less than 0.337nm Spacing and latitude of emulsion value is inlayed less than 1.0.
15. collector as described in claim 1, wherein the graphite film show degree of graphitization not less than 80% and/or Latitude of emulsion value is inlayed no more than 0.4.
16. collector as described in claim 1, wherein obtain the film in the following manner: in tropism control stress Under the influence of by the suspension of HA or HA and the mixture of graphene film deposit at least one described main surface with formed HA or The layer of the mixture of HA and graphene film, and the layer is then heat-treated under 500 DEG C of heat treatment temperature from 80 DEG C to 1.
17. collector as claimed in claim 16, wherein the heat treatment temperature is from 80 DEG C to 500 DEG C.
18. collector as claimed in claim 16, wherein the heat treatment temperature is from 80 DEG C to 200 DEG C.
19. collector as described in claim 1, wherein the film contains the chemically combined humic acid point being parallel to each other The humic acid and graphene planes that son or chemistry merge.
20. collector as described in claim 1, wherein the film is with the length not less than 5cm and not less than 1cm Width continuous length film.
21. collector as described in claim 1, wherein when independent measurement, the film or graphite film, which have, to be greater than The phsyical density of 1.6g/cm3 and/or tensile strength greater than 30MPa.
22. collector as described in claim 1, wherein when independent measurement, the film or graphite film, which have, to be greater than The phsyical density of 1.8g/cm3 and/or tensile strength greater than 50MPa.
23. collector as described in claim 1, wherein when independent measurement, the film or graphite film, which have, to be greater than 2.0g/cm3Phsyical density and/or tensile strength greater than 80MPa.
24. a kind of lithium rechargeable battery or lithium ion battery contain collector as described in claim 1 as anode collection Fluid and/or cathode current collector.
25. a kind of lithium rechargeable battery contains collector as described in claim 1 as anode collector or cathode collection Fluid, the lithium battery be lithium-sulphur battery core, lithium-selenium battery core, lithium sulphur/selenium battery core, lithium-air battery core, lithium-graphene battery core or Lithium-carbon battery core.
26. a kind of capacitor contains collector as described in claim 1 as anode collector or cathode current collector, institute State capacitor be symmetrical supercapacitor, asymmetric super capacitor electric core, hybrid super capacitor-battery battery core, Or lithium-ion capacitor battery core.
27. a kind of metal for generating for combining height-oriented humic sorrel used in the battery or supercapacitor The method of foil collector, which comprises
(a) it prepares humic acid (HA) or chemical functionalization humic acid (CHA) piece is scattered in dispersion in liquid medium, wherein The HA piece contains by weight of from more than 5% oxygen content or the CHA piece contains by weight of from more than 5% non-carbon element and contains Amount;
(b) HA the or CHA dispersion is distributed and is deposited at least one main surface of metal foil to form HA's or CHA Wet layer, wherein the distribution and deposition procedure include that the dispersion is made to be subjected to orientation induced stress;
(c) liquid medium is removed partially or even wholly from the wet layer of the HA or CHA to be formed with lonsdaleite plane With the interplanar spacing d for the 0.4nm to 1.3nm for such as passing through X-ray diffraction measure002HA or CHA layers of drying;And
(d) higher than be heat-treated under 80 DEG C of the first heat treatment temperature described dry HA or CHA layer continue time enough section with The metal foil collector of the height-oriented humic sorrel of the combination is generated, is substantially mutually put down wherein the humic acid film contains HA the or CHA piece of interconnection, merging or the thermal reduction of at least one main surface is gone and is chemically bonded to and is parallel to, And the humic sorrel, which has, is not less than 1.3g/cm3Phsyical density, at least the thermal conductivity of 250W/mK, and/or be not less than The conductivity of 500S/cm.
28. method as claimed in claim 27, further comprises step (e): being higher than first heat treatment temperature The metal foil that the combination humic sorrel is further heat-treated under second heat treatment temperature continues time enough section to generate knot The metal foil collector of graphite film is closed, wherein the graphite film has the interplanar spacing d less than 0.4nm002It is small by weight In 5% oxygen content or non-carbon element content;(f): compressing the graphite film to generate and have not less than 1.3g/cm3Object Manage density, at least thermal conductivity of 500W/mK, and/or the highly conductive property graphite film not less than the conductivity of 1,000S/cm.
29. method as claimed in claim 27, further comprise after the step (d) by the merging or also The step of humic acid membrane pressure contracting of former HA or CHA.
30. method as claimed in claim 27, wherein HA the or CHA dispersion further contains stone dispersed therein Black alkene piece or molecule, and the ratio of the HA and graphene or CHA and graphene is from 1/100 to 100/1 and the stone Black alkene is selected from raw graphite alkene, graphene oxide, the graphene oxide of reduction, fluorinated graphene, bromination graphene, iodate graphite Alkene, boron-doped graphene, adulterate the graphene of nitrogen, chemical functionalization graphene, or combinations thereof.
31. method as claimed in claim 30, further comprises step (e): by the merging or reduction HA or CHA Humic sorrel be higher than first heat treatment temperature the second heat treatment temperature under further heat treatment continue it is enough when Between section with generate have less than 0.4nm interplanar spacing d002Oxygen content or non-carbon element content by weight less than 5% Graphite film;With step (f): compressing the graphite film to generate and have not less than 1.6g/cm3Phsyical density, at least 700W/ The thermal conductivity of mK, and/or highly conductive property graphite film not less than the conductivity of 1,500S/cm.
32. method as claimed in claim 27, wherein HA the or CHA piece is to be in be enough the shape in the liquid medium At the amount of liquid crystalline phase.
33. method as claimed in claim 27, wherein the dispersion contains the first body being scattered in the liquid medium The HA or CHA of fraction, first volume fraction have been more than the critical volume fraction (V that liquid crystalline phase is formedc), and described point Granular media is concentrated to reach the second volume fraction of the HA or CHA that are greater than first volume fraction, is taken with improving HA or CHA piece To.
34. method as claimed in claim 33, wherein first volume fraction is equivalent to HA or CHA in the dispersion In by weight from 0.05% to 3.0% weight fraction.
35. method as claimed in claim 34, wherein before the step (b), the dispersion be concentrated into containing by Poidometer is higher than 3.0% but the HA or CHA that are scattered in the liquid medium less than 15%.
36. method as claimed in claim 27, wherein the dispersion further contain be dissolved in the liquid medium or It is attached to the polymer of the HA or CHA.
37. method as claimed in claim 27, wherein the CHA contains the chemical functional group selected from following item: polymer, SO3H、COOH、NH2, OH, R'CHOH, CHO, CN, COCl, halogen root, COSH, SH, COOR', SR', SiR'3、Si(--OR'--)yR'3-y、Si(--O--SiR'2--)OR'、R"、Li、AlR'2、Hg--X、TlZ2And Mg--X;Wherein, y is equal to or less than 3 Integer, R' are hydrogen, alkyl, aryl, naphthenic base or aralkyl, cyclophane base or poly- (alkyl ether), and R " is fluoro-alkyl, fluoro virtue Base, fluoro naphthenic base, fluoroaralkyl or cyclophane base, X are halogen roots, and Z be carboxylate radical or trifluoroacetic acid root, or combinations thereof.
38. method as claimed in claim 30, wherein the graphene film contains chemical functionalization graphene, the chemistry Functionalized graphite's alkene contains the chemical functional group selected from following item: polymer, SO3H、COOH、NH2、OH、R'CHOH、CHO、CN、 COCl, halogen root, COSH, SH, COOR', SR', SiR'3、Si(--OR'--)yR'3-y、Si(--O--SiR'2--)OR'、R"、Li、 AlR'2、Hg--X、TlZ2And Mg--X;Wherein, y is equal to or the integer less than 3, R' are hydrogen, alkyl, aryl, naphthenic base or virtue Alkyl, cyclophane base or poly- (alkyl ether), R " are fluoro-alkyl, fluorinated aryl, fluoro naphthenic base, fluoroaralkyl or cyclophane base, X is halogen root, and Z be carboxylate radical or trifluoroacetic acid root, or combinations thereof.
39. method as claimed in claim 28, wherein second heat treatment temperature is higher than 1,500 DEG C, is persistently enough to put down Spacing d between face002It is decreased to less than the value of 0.36nm and is decreased to be less than by weight by oxygen content or non-carbon element content 0.1% a period of time.
40. method as claimed in claim 27, wherein the liquid medium is made of the mixture of water or water and alcohol.
41. method as claimed in claim 27, wherein the liquid medium contains the non-aqueous solvent selected from following item: poly- Ethylene glycol, ethylene glycol, propylene glycol, alcohol, sugar alcohol, polyglycereol, glycol ethers, solvent amine-based, the solvent based on amide, carbonic acid are sub- Arrcostab, organic acid or inorganic acid.
42. method as claimed in claim 27, the method is roll-to-roll method, wherein the step (b) includes will be described The piece of metal foil is fed to crystallizing field from roller, and the layer of HA or CHA dispersion is deposited to at least one master of the metal foil The wet layer of the HA or CHA dispersion is formed on surface, the dry HA or CHA dispersion is deposited on gold to be formed Belong to HA or CHA layers of drying on foil surface, and collects the metal foil of the HA or CHA layers of deposition on collecting drum.
43. method as claimed in claim 27, wherein first heat treatment temperature contains in 100 DEG C -1,500 DEG C of range Interior temperature, and the height-oriented humic sorrel has the oxygen content less than 2.0%, between the interplanar less than 0.35nm Away from, be not less than 1.6g/cm3Phsyical density, at least thermal conductivity of 800W/mK, and/or the conductivity not less than 2,500S/cm.
44. method as claimed in claim 27, wherein first heat treatment temperature contains at 1,500 DEG C -2,100 DEG C of models Interior temperature is enclosed, and the height-oriented humic sorrel has the oxygen content less than 1.0%, the plane less than 0.345nm Between spacing, at least thermal conductivity of 1,000W/mK, and/or the conductivity not less than 5,000S/cm.
45. method as claimed in claim 28, wherein the described first and/or second heat treatment temperature contains greater than 2,100 DEG C Temperature, and the highly conductive property graphite film has oxygen content no more than 0.1%, between the graphene less than 0.340nm Spacing inlays latitude of emulsion value, at least thermal conductivity of 1,300W/mK, and/or the conductance not less than 8,000S/cm no more than 0.7 Rate.
46. method as claimed in claim 28, wherein second heat treatment temperature contains the temperature not less than 2,500 DEG C, And the highly conductive property graphite film have less than 0.336nm graphene between spacing, no more than 0.4 inlay latitude of emulsion value, Thermal conductivity greater than 1,500W/mK, and/or the conductivity greater than 10,000S/cm.
47. method as claimed in claim 28, wherein the highly conductive property graphite film shows the graphite not less than 80% Change degree and/or latitude of emulsion value is inlayed less than 0.4.
48. method as claimed in claim 27, wherein HA the or CHA piece has maximum original length, and the height The humic sorrel of orientation contains HA the or CHA piece that the length having is greater than the maximum original length.
49. method as claimed in claim 28, wherein the highly conductive property graphite film is that have as by the X-ray The polycrystalline graphite alkene structure of the preferred crystallite orientation of diffraction method measurement.
50. method as claimed in claim 30, wherein the heat treatment step (e) cause HA or CHA piece and other HA or CHA piece is connected chemically, merges or is chemically combined to form graphite-structure with graphene film.
51. method as claimed in claim 28, wherein the height-oriented graphite film has the electricity greater than 5,000S/cm Conductance, is greater than 1.9g/cm at the thermal conductivity greater than 800W/mK3Phsyical density, the tensile strength greater than 80MPa, and/or be greater than The elasticity modulus of 60GPa.
52. method as claimed in claim 28, wherein the height-oriented graphite film has the electricity greater than 8,000S/cm Conductance, is greater than 2.0g/cm at the thermal conductivity greater than 1,200W/mK3Phsyical density, the tensile strength greater than 100MPa, and/or Elasticity modulus greater than 80GPa.
53. method as claimed in claim 28, wherein the height-oriented graphite film has the electricity greater than 12,000S/cm Conductance, is greater than 2.1g/cm at the thermal conductivity greater than 1,500W/mK3Phsyical density, the tensile strength greater than 120MPa, and/or Elasticity modulus greater than 120GPa.
CN201780060219.2A 2016-08-22 2017-02-21 Metal foil film collector in conjunction with humic acid and the battery and supercapacitor containing it CN109792055A (en)

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US15/243,606 US20180053931A1 (en) 2016-08-22 2016-08-22 Humic acid-bonded metal foil film current collector and battery and supercapacitor containing same
US15/243,606 2016-08-22
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