CN109803820A - Conductibility foam and device derived from humic acid - Google Patents

Abstract

Foam derived from a kind of humic acid, it is made of multiple holes and hole wall, wherein the hole wall contains lonsdaleite atomic plane or piece derived from single layer or few layer humic acid, the lonsdaleite atomic plane that there is 2-10 layer heap to fold for few layer lonsdaleite atomic plane or piece, does the lonsdaleite atomic plane of the stacking have the interplanar spacing d such as the slave 0.3354nm to 0.40nm by X-ray diffraction measurement? 002#191, and by weight 0.01% to 25% non-carbon element is contained in the single layer or few layer lonsdaleite atomic plane, and wherein the humic acid selects autoxidizable humic acid, the humic acid of reduction, fluorinated humic acid, the humic acid of chlorination, brominated humic acid, the humic acid of iodate, the humic acid of hydrogenation, the humic acid of nitridation, the humic acid of doping, chemical functionalization Humic acid, or combinations thereof.

Description

Conductibility foam and device derived from humic acid

Cross reference to related applications

This application claims U.S. Patent Application No. 15/251,841 and 2016 on August 30, that August in 2016 is submitted on the 30th The priority of the U.S. Patent Application No. 15/251,849 of submission, these patent applications are incorporated herein by quoting mode.

Technical field

Present invention relates in general to the fields of carbon graphite foam, and relate more specifically to a kind of being derived from for new model The conductibility foam of humic acid, the device containing foam derived from this humic acid and its production method.

Background technique

There are five types of unique crystal structures, including diamond, fullerene (0-D nano-graphite material), carbon to receive for known carbon tool Mitron or carbon nano-fiber (1-D nano-graphite material), graphene (2-D nano-graphite material) and graphite (3-D graphite material Material).Other than fullerene, foaming structure can be made in all these materials.

Carbon nanotube (CNT) refers to the tubular structure with single wall or multi wall growth.Carbon nanotube (CNT) and carbon nano-fiber (CNF) with about several nanometers to several hundred nanometers of diameter.Its longitudinal, hollow structure assign the unique mechanical, electricity of material and Chemical characteristic.CNT or CNF is one-dimensional nano carbon or 1-D nano-graphite material.However, CNT is difficult to produce and is extremely expensive 's.Furthermore it is known that CNT is difficult to disperse in solvent or water and is difficult to mix with other materials.These features seriously limit Its application range is made.

Single-layer graphene film is made of the carbon atom for occupying two-dimentional hexagoinal lattice.Multi-layer graphene is by more than one graphite The platelet that alkene plane is constituted.Individual single-layer graphene film and multi-layer graphene platelet are collectively referred to herein as nano-graphene piece Brilliant (NGP) or grapheme material.NGP include raw graphite alkene (substantially 99% carbon atom), slight oxidation graphene (press The oxygen of poidometer<5%) and graphene oxide (oxygen by weight>=5%).

It has been found that NGP has a series of uncommon physics, chemistry and mechanical property.Our research group finds at first Graphene [B.Z.Jang and W.C.Huang, " Nano-scaled Graphene Plates [nanoscale graphite alkene plate] ", 2002 The U.S. Patent Application No. 10/274,473 that October 21 in year submits；It is now U.S. Patent number 7,071,258 (07/04/2006)]. Previously, we reviewed method [Bor Z.Jang and the A Zhamu, " Processing of production NGP and NGP nanocomposite Of Nano Graphene Platelets (NGPs) and NGP Nanocomposites:AReview [nano-graphene platelet : summary] ", (NGP) and the processing of NGP nanocomposite J.Materials Sci. [material science magazine] 43 (2008) 5092-5101].Four kinds of main art methods have been followed to produce NGP.It the advantages of summarizing them as follows and lacks Point:

Method 1: the chemistry of graphene oxide (GO) is formed and reduction

First method (Fig. 1) needs natural with intercalator and oxidant (for example, the respectively concentrated sulfuric acid and nitric acid) processing Graphite powder is to obtain graphite intercalation compound (GIC) or actually graphite oxide (GO).[William S.Hummers, Jr. etc. People, Preparation of Graphitic Oxide [preparation of graphite oxide], Journal of the American Chemical Society [American Chemical Society], page 1958,1339].Before intercalation or oxidation, graphite has about Spacing (L between the graphene planes of 0.335nm_d=1/2d₀₀₂=0.335nm).In the case where intercalation and oxidation processes, graphite Spacing increases to the typically greater than value of 0.6nm between alkene.This is the first expansion that graphite material is undergone during the chemical route Stage.Then the graphene layer extruding (exfoliation) of the ultrasonic treatment auxiliary using thermal shock exposure method or based on solution Method makes gained GIC or GO be subjected to further expanding (commonly referred to as extruding).

In thermal shock exposure method, so that GIC or GO is exposed to high temperature (typically 800 DEG C -1,050 DEG C) and continue short time period (typically 15 to 60 seconds) so that GIC or GO extruding or expansion with the graphite of expansion that form extruding or further, the graphite allusion quotation Type in the form of " graphite worm " being made of graphite flake still interconnected amongst one another.This thermal shock program can produce Isolated graphite flake or graphene film, but usually most of graphite flake keeps interconnection.Typically, it is then ground using air Mill, mechanical shearing or ultrasonic treatment in water make the graphite of extruding or graphite worm be subjected to thin slice separating treatment.Therefore, method 1 substantially needs three different programs: the first expansion (oxidation or intercalation), further expansion (or " extruding ") and separation.

In the partition method based on solution, expansion or extruding GO powder is dispersed in water or alcohol solution, it is made It is subjected to being ultrasonically treated.It is important to note that, in these methods, (that is, in the first expansion after the intercalation of graphite and oxidation Ultrasonic treatment is used (after the second expansion) after the thermal shock exposure of gained GIC or GO later) and typically.Substitution Property, so that the GO powder being dispersed in water is subjected to ion exchange or interminable purifying procedure, mode is so that being present in plane Between repulsive force between ion in space surpass the Van der Waals force between graphene, cause graphene layer to separate.

In the presence of several main problems relevant to this conventional chemical production method:

(1) this method is needed using a large amount of several undesirable chemicals, such as sulfuric acid, nitric acid and potassium permanganate or Sodium chlorate.

(2) chemical treating process needs long intercalation and oxidization time, typically 5 hours to 5 days.

(3) during this prolonged intercalation or oxidation process, strong acid (will by " corroding its path for entering graphite " Graphite is converted into the carbon dioxide lost in the process) and consume a large amount of graphite.Lose the immersion of 20%-50% by weight Graphite material in strong acid and oxidant is not uncommon for.

(4) hot extruding needs high temperature (typically 800 DEG C -1,200 DEG C), and is therefore highly energy intensive method.

(5) heat-and solution-induction extruding method require very cumbersome washing and purification step.For example, typically making 1 gram of GIC is washed and recycled with the water of 2.5kg, generates the waste water for largely needing proper treatment.

(6) in heat-and solution-induction extruding method the two, products therefrom is GO platelet, these GO platelets are subjected to Further electronation processing is to reduce oxygen content.Typically, or even after reduction, the conductivity of GO platelet is still far below primary The conductivity of graphene.In addition, reducing program is often referred to using toxic chemical, such as hydrazine.

(7) 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 stayed, which decompose, generates various undesirable sulfur-bearings and containing nitrogen compound (for example, NO_xAnd SO_x).Stream Object needs expensive regulation program out, so as not to unfavorable environment influence.

Method 2: the direct formation of primary nano-graphene platelet

In 2002, our research team was successfully from the partially carbonized or graphite obtained by polymer or pitch precursor Isolate single layer and multi-layer graphene piece [B.Z.Jang and W.C.Huang, " Nano-scaled in the polymerization carbon of change Graphene Plates [nanoscale graphite alkene plate] ", the U.S. Patent Application No. 10/274 that on October 21st, 2002 submits, 473；It is now U.S. Patent number 7,071,258 (07/04/2006)].Mack et al. [" Chemical manufacture of Nanostructured materials [the chemistry manufacture of nano structural material] " U.S. Patent number 6,872,330 (2005 3 The moon 29)] a kind of method is developed, this method is related to potassium melt intercalation graphite and connects the graphite of gained K- intercalation with alcohol Touching produces the violent expanded graphite containing NGP.This method must carefully be carried out in vacuum or in extremely dry glove box environment, because Pure alkali metals such as potassium and sodium are extremely sensitive to moisture and have explosion danger.The method is unsuitable for mass production NGP.

Method 3: epitaxial growth and chemical vapor deposition of the nano-graphene piece on mineral crystal surface

Ultra-thin stone on base material can be obtained by epitaxial growth based on thermal decomposition and laser desorption-ionization technology The small-scale production of black alkene piece.[Walt A.DeHeer,Claire Berger,Phillip N.First,"Patterned Thin film graphite devices and method for making same [patterned film graphite device and its Manufacturing method] " U.S. Patent number 7,327,000B2 (on June 12nd, 2003)] have outside the graphite of only one or several atomic layers Prolong film due to its characteristic feature and as device device substrate very high potential and there is technology and scientific importance.However, these Method is unsuitable for the isolated graphene film of mass production for composite material and stored energy application.

It is in another method of graphene of form of film (typically thickness < 2nm) is catalytic chemical vapor for producing Sedimentation.Catalysis CVD is related to appropriate hydrocarbon gas (for example, C₂H₄) catalytic decomposition on the surface Ni or Cu to be to form single layer or few layer Graphene.In the case where Ni or Cu are catalyst, will via at a temperature of 800 DEG C -1,000 DEG C decomposing hydrocarbon gas molecule obtain Carbon atom be deposited directly on Cu foil surface or precipitate on Ni foil surface from Ni-C solid solution state, to form single layer or few Layer graphene (being less than 5 layers) piece.Ni- or Cu- catalysis CVD method be not suitable for depositing more than 5 graphene planes (typically < 2nm), more than 5 graphene planes, Ni or Cu layers below cannot provide any catalytic effect again.CVD graphene film is very Expensive.

Method 4: method from bottom to top (by small molecule synthesizing graphite alkene)

Yang et al. [" Two-dimensional Graphene Nano-ribbons [two-dimensional graphene nanobelt], " J.Am.Chem.Soc. [American Chemical Society] 130 (2008) 4216-17] use following methods composition length for most 12nm's Nano-graphene piece, this method is with Isosorbide-5-Nitrae-two iodo- 2, the Suzuki-Gong Pu of 3,5,6- tetraphenyls-benzene and 4- bromobenzeneboronic acid (Suzuki-Miyaura) coupling starts.Gained hexaphenyl benzene derivatives, which are further derivatized, is fused into small graphene with ring Piece.This is the slow method for producing minimum graphene film so far.

Therefore, there is an urgent need to a new class of carbon nanomaterial, the nano material is suitable or excellent with graphene for characteristic In graphene, but can more cost-effectively, more quickly, more can scale and in more environmental-friendly mode Production.Production method for this new carbon nanomaterial need reduction amount undesirable chemicals (or all eliminate this A little chemicals), process time for shortening, less energy consumption, the undesirable chemical species reduced or eliminated enter discharge System (for example, sulfuric acid) enters air (for example, SO₂And NO₂) discharge.In addition, should be readily able to receive this new Relatively thermally conductive and conductive foaming structure is made in rice material.

In general, foam or foamed material are made of hole (or abscess) and hole wall (solid material).This some holes can be mutual Even to form open celled foam.As example, hole wall of the grapheme foam by hole and containing grapheme material is constituted.There are three kinds of lifes The main method of grapheme foam is produced, all of which is cumbersome, energy consumption and slow:

First method is hydrothermal reduction graphene oxide hydrogel, which typically relates to graphene oxide (GO) aqueous suspension be sealed in autoclave and at high pressure (tens of or hundreds of atm), at typically 180 DEG C DEG C -300 DEG C The GO suspension is heated into extended period (typically 12-36 hours) at a temperature in the range of DEG C.The useful ginseng of the method It examines document to provide herein: Y.Xu et al. " Self-Assembled Graphene Hydrogel via a One-Step Hydrothermal Process [via the graphene hydrogel of the self assembly of one step hydro thermal method] " ACS Nano [ACS nanometers] 2010,4,4324-4330.In the presence of several main problems associated with the method: (a) high pressure requirement makes it be for industry Unpractical method of large-scale production.Firstly, the method cannot carry out on a continuous basis.(b) it is difficult to (if not It executes if possible) to the aperture of gained porous structure and the control of porosity level.(c) the oxidation stone of the reduction obtained by change Do not have flexibility (for example, the material cannot be made into film shape) in terms of the shape and size of black alkene (RGO) material.(d) should Method is related to the GO (for example, 2mg/mL=2g/L=2kg/kL) using the super low concentration in water that suspends.Removing non-carbon member Element (in the case where most 50%), only can produce grapheme material (RGO)/1000 liter suspension less than 2kg.In addition, practical On can not operate the 1000 liters of reactors that must endure as high temperature and high pressure condition.It is clear that there is no be used for mass production Porous graphene structure can scalable process.

Second method is the catalysis CVD method based on template auxiliary, and this method is related to sacrificing graphene CVD deposition In template (such as Ni foam).Grapheme material meets the shape and size of Ni foaming structure.Then fallen using etchant etching Ni foam leaves the monolith graphene skeleton of substantially open celled foam.The useful bibliography of the method provides herein: Zongping Chen et al., " Three-dimensional flexible and conductive interconnected Graphene networks grown by chemical vapour deposition [passes through chemical vapor deposition growth Three-dimension flexible and conductive interconnection graphene network] ", Nature Materials [nature material], 10 (in June, 2011) 424-428.There are problems that it is associated with this method several: (a) be catalyzed CVD be inherently it is slowly, height consumes Energy and expensive method；(b) it is dirty that etchant, which is typically highly undesirable chemicals and gained etching solution containing Ni, The source of dye.It is extremely difficult and expensive for recycling or recycle the Ni metal of dissolution from etchant solutions.(c) when Ni steeps The shape and size of grapheme foam are maintained to be challenging when foam is etched without damaging cell wall.Gained graphene Foam is typically highly brittle and frangible.(d) it may be tired for cvd precursor gas (such as hydrocarbon) being transferred to inside metal foam Difficult, lead to uneven texture, because certain points of sacrificial metal foam inside may be that cvd precursor gas is inaccessible.

The third method of production grapheme foam also utilizes expendable material (such as colloid granules of polystyrene, PS), should Expendable material is coated with graphene oxide sheet using self-assembly method.For example, Choi et al. prepares the graphite of chemical modification in two steps Alkene (CMG) paper: stand alone type is manufactured by the aqueous soliquid of mixing of vacuum filter CMG and PS (2.0 μm of PS spheres) PS/CMG film, then removes

PS pearl generates 3D macropore [B.G.Choi et al., " 3D Macroporous Graphene Frameworks for Supercapacitors with High Energy and Power Densities is [for having high-energy and power density Supercapacitor 3D macropore graphene frame] ", ACS Nano [ACS nanometers], 6 (2012) 4020-4028.].Choi etc. People is by the free-standing PS/CMG paper of filtering manufacture well-ordering, and the manufacture is to be prepared separately negatively charged CMG colloid and positively charged The PS suspension of lotus starts.It disperses the mixture of CMG colloid and PS suspension in the solution under controlled pH (=2), In two kinds of compound surface charges having the same (zeta potential value for CMG be+13 ± 2.4mV and for PS be+68 ± 5.6mV).When pH is increased to 6, the CMG (± 3.7mV of zeta potential=- 29) and PS the sphere (± 2.5mV of zeta potential=+ 51) are due to it Between electrostatic interaction and hydrophobic character and assemble, and these then pass through filtering techniques integrally chemical conversion PS/CMG Composite paper.The method also has the shortcomings that several: (a) the method needs to carry out both graphene oxide and PS particle non- Often cumbersome chemical treatment.(b) removing PS by toluene also causes macroporous structure to die down.(c) toluene is the chemistry of height control It product and extremely must carefully handle.(d) aperture is typically excessive (such as several μm), for many useful applications Yan Tai great.

The every kind of art methods or technique described above explicitly indicated that for producing graphene and grapheme foam All have main defect.Therefore, the purpose of the present invention is to provide a new class of electrically and thermally conductive and machine robust foams Material, and a kind of cost-efficient method for producing this class A foam A is provided.

Humic acid (HA) is typically found in the organic substance in soil, and alkali (such as KOH) can be used from soil Middle extraction.HA can also be extracted from a type of coal for being known as leonardite with high yield, which is lignite High oxidation pattern.The HA extracted from leonardite contain largely be located at graphene-like molecular center (lonsdaleite structure SP²Core) perimeter oxygen-containing group (such as carboxylic group).This material and the strong acid oxidation production by natural graphite Graphene oxide (GO) is slightly similar.HA has typical by weight 5% to 42% oxygen content, and (other main elements are Carbon and hydrogen).After electronation or thermal reduction, HA has by weight 0.01% to 5% oxygen content.For in the application Claim limit purpose, humic acid (HA) refers to by weight from 0.01% to 42% whole oxygen content ranges.Reduction Humic acid (RHA) be with by weight 0.01% to 5% oxygen content specific type HA.

The present invention is directed to a new class of graphene-like 2D material (that is, humic acid), can unexpectedly be converted into tool There is the foaming structure of high structural intergrity.Therefore, another purpose is to provide a kind of for this nanometer carbon foam of mass production The cost-efficient method of (specifically, foam derived from humic acid).The method is not related to the disagreeableness chemistry of use environment Product.The method makes it possible to flexible design and control porosity level and aperture.

It is a further object to provide foam derived from a kind of humic acid, show with ordinary graphite foam, The suitable or bigger thermal conductivity of those of carbon foam or grapheme foam, conductivity, elasticity modulus, and/or intensity.The present invention Another purpose again be to provide foam derived from a kind of humic acid, with mesoscale pore diameter range (2-50nm).

It is a further object to provide the products (such as device) containing foam derived from humic acid of the invention With the method for operating these products.

Summary of the invention

The present invention provides foams derived from a kind of humic acid, are made of multiple holes and hole wall, wherein the hole wall contains There is lonsdaleite piece derived from single layer or few layer humic acid, and few layer lonsdaleite piece has the lonsdaleite of 2-10 stacking former Sub- plane, the plane have such as the slave 0.3354nm to 0.60nm by X-ray diffraction measurement (preferably not more than Interplanar spacing d 0.40nm)₀₀₂.The single layer or few layer lonsdaleite piece contain by weight 0.01% to 25% non-carbon member Element.Humic acid (HA) selects autoxidizable humic acid, the humic acid of reduction, fluorinated humic acid, the humic acid of chlorination, brominated corruption Grow acid, the humic acid of iodate, the humic acid of hydrogenation, the humic acid of nitridation, the humic acid of doping, chemical functionalization humic acid, Or combinations thereof.

The foam derived from the humic acid of the invention can be divided into three types: (a) containing at least 10% (allusion quotation by weight Type by weight from 10% to 42%, and most typically from 10% to 25%) the non-carbon that can be used for wide range of application (wherein original humic acid molecule is kept essentially constant humic acid (HA) foam of element, but someization between HA molecule It learns connection to have occurred and that)；(b) foam for the humic acid for merging and restoring based on chemistry, wherein extensive between original HA molecule Connection and merging have occurred and that form the starting graphite alkene shape lonsdaleite piece for being constituted hole wall, are attached initially to so as to cause containing The chemical species of non-carbon element on HA molecule release (therefore, non-carbon element content be reduced to usually by weight 2% with Between 10%)；And (c) all substantially only containing carbon (non-carbon content by weight < 2%, preferably < 1%, and into One step is preferably < 0.1%) humic acid derived from graphite foam, middle hole wall contain for lonsdaleite atomic plane single layer or Few layer (2-10) graphene-like piece.

Preferably and typically, foam derived from HA has from 0.005g/cm³To 1.7g/cm³Density, from 50m²/g To 3,200m²Specific surface area, the per unit specific gravity at least thermal conductivity of 100W/mK, and/or per unit specific gravity of/g is not less than The conductivity of 500S/cm.More typically, foam derived from humic acid has from 0.01g/cm³To 1.5g/cm³Density or from The average pore size of 2nm to 50nm.In one embodiment, which has from 200m²/ g to 2,000m²The specific surface area of/g or From 0.1g/cm³To 1.3g/cm³Density.

Typically, if foam derived from HA is raw by the method without containing the heat treatment temperature (HTT) higher than 300 DEG C DEG C It produces, then the foam has the non-carbon element content in 10% to 42% range by weight.These hole walls still can contain For the identifiable humic acid molecule of sheet lonsdaleite atomic structure.Non-carbon element may include the element selected from the following terms: Oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen or boron.In a specific embodiment, hole wall contains fluorination humic acid and the foam contains By weight from 0.01% to 25% fluorine content.In another embodiment, the foam contain by weight from 0.01% to 25% oxygen content.

In the case where being higher than 300 DEG C DEG C of HTT, tightly packed and well-arranged adjacent HA molecule can be connected chemically Together to form the polycyclic aromatic structure for being similar to starting graphite alkene shape lonsdaleite atomic structure.As heat treatment continues, this A little height aromatic molecules are merged in a manner of edge-to-edge to increase the length and width of six side's plane of graphene-like, and same When, several lonsdaleite planes can be stacked to form multilayer atomic structure of carbon similar with few layer graphene-structured.It is flat Spacing is typically reduced to < < 0.60nm, more typically < 0.40nm between face.If HTT be from 300 DEG C DEG C up to 1,500 DEG C DEG C, The foam for the humic acid for merging and restoring based on chemistry is then typically produced, wherein extensive connection and conjunction between original HA molecule And it has occurred and that form the starting graphite alkene shape lonsdaleite piece for being constituted hole wall.Non-carbon element in the foam is typically reduced to From 2% to 10%.

If HTT is from 1,500 DEG C DEG C to 3,200 DEG C DEG C, then the foam can essentially become graphite foam, mesoporous Wall contains single layer or few layer graphene-like lonsdaleite plane, and non-carbon content is reduced to by weight less than 2%.

In a preferred embodiment, which is made continuous length roll film (roll sheet) form (continuous bubble The volume of foam piece), the continuous length roll film form have no more than 200 μm thickness and it is at least 1 meter long, preferably at least 2 meters, into Preferably at least 10 meters of one step and most preferably at least 100 meters of length.This piece volume is generated by roll to roll.It is not present Graphene-like foam derived from the HA of the prior art of piece roll form is made.

In a preferred embodiment, there is foam derived from HA oxygen content or non-carbon by weight less than 1% to contain Amount, and hole wall has graphene-like plane, the per unit specific gravity at least thermal conductivity of 200W/mK, and/or the per unit ratio stacked It is not less than the conductivity of 1,000S/cm again, these graphene-like planes have the interplanar spacing less than 0.35nm.

In another preferred embodiment, foam derived from HA has by weight less than 0.1% oxygen content or non- Carbon content, and the hole wall contains the graphene-like lonsdaleite atomic plane of stacking, the per unit specific gravity at least heat of 250W/mK Conductance, and/or per unit specific gravity are not less than the conductivity of 1,500S/cm, these graphene-like lonsdaleite atomic planes have small In the interplanar spacing of 0.34nm.

In another preferred embodiment again, grapheme foam have oxygen content by weight no more than 0.01% or Non-carbon content, and the hole wall contain stacking graphene-like plane, no more than 0.7 inlay latitude of emulsion value, per unit specific gravity At least conductivity of the thermal conductivity of 300W/mK, and/or per unit specific gravity not less than 2,000S/cm, these graphene-like planes tool There is spacing between the graphene less than 0.336nm.

In still another preferred embodiment, grapheme foam has containing the graphene-like atomic plane stacked, no The thermal conductivity of latitude of emulsion value, per unit specific gravity greater than 400W/mK, and/or per unit specific gravity are inlayed greater than 3,000S/ greater than 0.4 The hole wall of the conductivity of cm, these graphene-like atomic planes have the interplanar spacing less than 0.336nm.

In a preferred embodiment, the graphene-like lonsdaleite atomic plane and be less than that these hole walls contain stacking 1.0 inlay latitude of emulsion value, these graphene-like lonsdaleite atomic planes have the interplanar spacing less than 0.337nm.At one In preferred embodiment, which is shown not less than the degree of graphitization of 80% (preferably no less than 90%) and/or less than 0.4 Inlay latitude of emulsion value.In a preferred embodiment, these hole walls contain the 3D of interconnection graphene-like lonsdaleite atomic plane Network.

In a preferred embodiment, which contains the mesoscale hole with the aperture from 2nm to 50nm.It should Solid foam can also be made into containing micron order hole (1-500 μm).

Foam derived from HA of the invention can be by including that the method for the following terms produces: (a) preparation has and is dispersed in The humic acid dispersion of multiple humic acid molecules or piece in liquid medium, wherein the humic acid selects autoxidizable humic acid, goes back Former humic acid, fluorinated humic acid, the humic acid of chlorination, brominated humic acid, the humic acid of iodate, hydrogenation humic acid, The humic acid of nitridation, the humic acid of doping, chemical functionalization humic acid, or combinations thereof, and wherein the dispersion contain appoint The foaming agent of choosing, with the foaming agent and humic acid weight ratio from 0/1.0 to 1.0/1.0；(b) the graphene dispersion body is distributed With deposit to supporting base material (such as plastic foil, sheet rubber, metal foil, sheet glass, scraps of paper etc.) surface on grown with forming web rot Acid layer；(c) part in acid layer is grown from the web rot or completely remove the liquid medium, to form dry humic acid layer；And (d) exist To be enough from non-carbon element (such as O, H, N, B, F, Cl, Br, I under the first heat treatment temperature from 80 DEG C DEG C to 3,200 DEG C DEG C Deng) cause escaping gas molecule formed and release or Activation of blowing agent the desired rate of heat addition be heat-treated the drying corruption Acid layer is grown to produce foam derived from humic acid.Preferably, the distribution and deposition procedure include being subjected to the humic acid dispersion It is orientated induced stress.

If HA material have by weight not less than 5% (preferably no less than 10%, be further preferably not less than 20%, it is not needed then not less than non-carbon element (such as O, H, N, B, F, Cl, Br, I etc.) content 30%) even more preferably The optional foaming agent.The subsequent high-temperature process is used to remove the major part in these non-carbon elements from the edge of HA molecule, To generate the escaping gas species for generating hole or abscess in solid foam structure.In other words, quite unexpectedly, this A little non-carbon elements play foaming agent.Therefore, the foaming agent of external addition is optional (being not required).However, using Foaming agent can provide desired application the flexibility of additional adjusting or adjustment porosity level and aperture.If humic Non-carbon element content in acid then typically needs foaming agent less than 5%.

The foaming agent can be physical blowing agent, chemical foaming agent, its mixture, dissolution and leaching agent or be mechanically induced Foaming agent.

This method may further include the heat treatment under the second heat treatment temperature for being higher than first heat treatment temperature should The step of solid foam, the step are persistently enough to obtain the graphene-like bubble for the lonsdaleite atomic plane that its middle hole wall contains stacking A period of time of foam, these lonsdaleite atomic planes stacked have the interplanar spacing d from 0.3354nm to 0.40nm₀₀₂With By weight less than the non-carbon element content of 5% (typically from 0.001% to 2%).When resulting non-carbon element content be from When 0.1% to 2.0%, interplanar spacing d₀₀₂Typically from 0.337nm to 0.40nm.

If the original HA molecule in dispersion contains by weight of from more than 5% non-carbon element content, solid foam In lonsdaleite atomic plane (after the heat treatment) contain fault of construction caused by during the heat treatment step (d).Liquid is situated between Matter can be simply water and/or alcohol, environmentally friendly.

In a preferred embodiment, this method is roll to roll, and wherein step (b) and (c) include by supporting base material Crystallizing field is fed to from feed roller, continuously or intermittently deposits to HA dispersion on the surface of the supporting base material with shape on it It is to form dry HA material layer and dry in the supporting base material by being deposited at wet HA material layer, the dry wet HA material layer Dry HA material layer is collected on collecting drum.This reel-to-reel or reel-to-reel method are truly commercial scale, large-scale system Method is made, can be automated.

In one embodiment, which is from 100 DEG C DEG C to 1,500 DEG C DEG C.In another embodiment In, which, which includes at least, is selected from (A) 300 DEG C DEG C -1,500 DEG C DEG C, 1,500 DEG C DEG C -2 of (B), 100 DEG C DEG C, And/or the temperature of 2,100 DEG C DEG C -3,200 DEG C DEG C of (C).In a specific embodiment, which is included in 300 DEG C DEG C -1, constant temperature at least 1 hour within the scope of 500 DEG C DEG C, and then at 1,500 DEG C DEG C -3,200 DEG C of DEG C of ranges Interior constant temperature at least 1 hour.

To dry HA layer carry out the first and/or second heat treatment have it is several unexpected as a result, and different heat Temperature ranges enable us to realize different purposes, and such as (a) removes non-carbon element from HA material and (such as heat-treat Fluorination humic acid is to obtain reduction humic acid), this generates escaping gas to generate hole or abscess in HA foam, (b) activates Chemically or physically humic acid molecular chemistry (c) is connected or is merged into height aromatic molecules simultaneously to generate hole or abscess by foaming agent And edge-to-edge merges aromatic ring structure or lonsdaleite plane to dramatically increase graphene-like in foam wall (solid portion of foam) The lateral dimension (length and width) of lonsdaleite piece (d) repairs naturally occurring or the fluorination in humic acid molecule, oxygen in HA The defect generated in change or nitridation process, and (e) reorganize and improve graphite domain or graphite crystal.These different mesh Or function reach different degrees of within the scope of different temperatures.Non-carbon element typically comprises the element selected from the following terms: oxygen, Fluorine, chlorine, bromine, iodine, nitrogen, hydrogen or boron.Quite it was unexpectedly determined that even if being heat-treated under low temperature foaming condition also often with side The mode (some in a manner of aspectant) of opposite side causes being connected chemically, merge or being chemically bonded between sheet HA molecule.

In one embodiment, foam derived from HA has from 200m²/ g to 2,000m²The specific surface area of/g.In a reality It applies in example, solid foam has from 0.1g/cm³To 1.5g/cm³Density.In one embodiment, in the first heat treatment temperature The step of lower heat treatment HA material layer (d), carries out under compressive stress.In another embodiment, this method includes compression step To reduce thickness, aperture or the porosity level of the film of foam derived from HA.In some applications, which has and is not more than 200 μm of thickness.

In one embodiment, the HA dispersion have dispersion by weight at least 5% HA in liquid medium with Form liquid crystalline phase.In one embodiment, the first heat treatment temperature contains the temperature within the scope of 80 DEG C DEG C -300 DEG C DEG C, and As a result, HA foam has the oxygen content or non-carbon element content less than 5%, and hole wall has the plane less than 0.40nm Between spacing, the thermal conductivity of per unit specific gravity at least 150W/mK (more typically at least 200W/mk), and/or per unit specific gravity it is not small In the conductivity of 1,000S/cm.

In a preferred embodiment, which contains in 300 DEG C DEG C -1,500 DEG C of DEG C range Interior temperature, and as a result, foam derived from HA has the oxygen content or non-carbon content less than 2%, and hole wall is with small It is not less than 1 in interplanar spacing, per unit the specific gravity at least thermal conductivity of 250W/mK, and/or per unit specific gravity of 0.35nm, The conductivity of 500S/cm.

When first and/or second heat treatment temperature contains the temperature within the scope of 1,500 DEG C DEG C -2,100 DEG C DEG C, HA Derivative foam has an oxygen content or non-carbon content less than 1%, and hole wall have spacing between the graphene less than 0.34nm, Per unit the specific gravity at least thermal conductivity of 300W/mK, and/or per unit specific gravity are not less than the conductivity of 3,000S/cm.

When first and/or second heat treatment temperature contains the temperature greater than 2,100 DEG C DEG C, foam derived from HA has Oxygen content or non-carbon content no more than 0.1%, and hole wall have less than 0.336nm interplanar spacing, no more than 0.7 Inlay the conductance that latitude of emulsion value, per unit the specific gravity at least thermal conductivity of 350W/mK, and/or per unit specific gravity are not less than 3,500S/cm Rate.

If first and/or second heat treatment temperature contains the temperature not less than 2,500 DEG C DEG C, then foam derived from HA Latitude of emulsion value and per unit specific gravity are inlayed greater than 400W/ with the graphene-like lonsdaleite plane containing stacking, no more than 0.4 The hole wall of conductivity of the thermal conductivity, and/or per unit specific gravity of mK greater than 4,000S/cm, these graphene-like lonsdaleite planes With the interplanar spacing for being less than 0.336nm.

In one embodiment, the graphene-like lonsdaleite plane that these hole walls contain stacking and the exhibition of inlaying less than 1.0 Angle value, these graphene-like lonsdaleite planes have the interplanar spacing less than 0.337nm.In another embodiment, HA spreads out The solid wall part of raw foam shows the degree of graphitization not less than 80% and/or inlays latitude of emulsion value less than 0.4.Again another In one embodiment, the solid wall part of foam derived from HA shows degree of graphitization not less than 90% and/or no more than 0.4 Inlay latitude of emulsion value.

Typically, the hole wall after being heat-treated at the HTT higher than 2,500 DEG C DEG C, in graphite foam derived from HA 3D network containing the interconnection lonsdaleite atomic plane for electronics conduction path.Cell wall contains graphite domain or graphite crystal, Lateral dimension (the L having_a, length or width) and not less than 20nm, more typical and preferably not less than 40nm, even more typically and preferably Not less than 100nm, even more typically and preferably not less than 500nm, it is frequently larger than 1 μm, and sometimes more than 10 μm.These graphite domains Typically there is from 1nm to 20nm, more typically from 1nm to the 10nm and further thickness more typically from 1nm to 4nm.

Preferably, foam derived from HA, which contains, has from 2nm to 50nm (the mesoscale of preferably 2nm to the aperture of 25nm) Hole.

In a preferred embodiment, the present invention provides a kind of for producing the solid being made of multiple holes and hole wall The roll to roll of foam derived from HA foam or HA.This method comprises: (a) preparation has the multiple corruption of dispersion in liquid medium The humic acid dispersion of acid molecule or piece is grown, wherein the humic acid selects autoxidizable humic acid, the humic acid of reduction, fluorinated corruption Grow acid, the humic acid of chlorination, brominated humic acid, the humic acid of iodate, the humic acid of hydrogenation, nitridation humic acid, doping Humic acid, chemical functionalization humic acid, or combinations thereof, and wherein the dispersion contains optional foaming agent, has from 0/ 1.0 to 1.0/1.0 foaming agent and humic acid weight ratio；(b) continuously or intermittently branch is distributed and deposited to the HA dispersion To form wet HA material layer on the surface of support group material, wherein the supporting base material is the continuous film supplied from feed roller and collection On collecting drum；(c) grow in acid layer part from the web rot or completely remove the liquid medium, with a heating zone or it is multiple plus Dry humic acid layer is formed in hot-zone；And (d) these heating zones containing heating temperature from 80 DEG C DEG C to 500 DEG C DEG C it Have to produce from 0.01g/ in one with the dry humic acid layer of desired rate of heat addition heat treatment for being enough to activate the foaming agent cm³To 1.7g/cm³Density or from 50m²/ g to 3,000m²Foam derived from the humic acid of the specific surface area of/g.In the method In, heat treatment occurs in situ in reel-to-reel program process.This is the cost-efficient method of height, is twined suitable for mass production It is wound up on a roller to be easy to transport and handle and be subsequently easy to graphite foam sheets derived from cutting and longitudinal sectional HA.

Orientation induced stress can be shear stress.As example, shear stress can be simple as " doctor blade " It is encountered in the case where list, guides HA dispersion on plastics or glass surface with sufficiently high during manual casting process Shear rate is sprawled.As another example, effective orientation induced stress is generated in automatic reel-to-reel coating procedure, wherein " roller serves as a contrast knife (knife-on-roll) " configuration is by the distribution of graphene dispersion body on mobile solid substrate (such as plastic foil). Relative motion between the moving film and coating knife is for realizing graphene film along the orientation in shear stress direction.Comma coating and The coating of slit coventry type die head coventry is the particularly effective method for this function.

Due to have surprisingly been observed that shear stress enable HA molecule or piece along specific direction (such as X-direction or Length direction) to generate preferred orientation and promote the contact between HA molecule or piece along foam wall, this orientation is lured for alignment Leading is most important step in the production of stress foam derived from HA of the invention.Further it was unexpectedly determined that these Preferred orientation and improved HA contacted with HA promote in the subsequent heat treatment process of dry HA layer HA molecule or piece it Between chemistry merge or connection.This kind of preferred orientation and improved contact are for finally realizing the different of foam derived from gained HA Often high thermal conductivity, conductivity, elasticity modulus and mechanical strength is vital.In general, being lured in no this shear stress In the case where the tropism control led, these fabulous characteristics cannot be obtained.

The present invention also provides a kind of oil removing or the devices of separation oil, and it is oily as absorbing to contain foam derived from humic acid Element.Additionally provide it is a kind of except solvent or separate solvent device, contain foam derived from humic acid as lyosoption Or the element of separation solvent.

The present invention also provides a kind of methods for separating oil with water.Method includes the following steps: (a) provides absorption The element of oil, which includes foam derived from integral type humic acid；(b) contact oil-aqueous mixtures with the element, the element Oil is absorbed from the mixture；(c) element is recalled from the mixture and extract the oil from the element；And it (d) reuses The element.

In addition, that the present invention provides one kind is organic molten for separating from solvent-water mixture or from multi-solvent mixture The method of agent.Method includes the following steps: (a) provides the element for absorbing organic solvent or separating solvent, which includes one Foam derived from body formula humic acid；(b) make the element molten with organic solvent-aqueous mixtures or containing the first solvent and at least second The multi-solvent mixture of agent contacts；(c) make the element from the mixture absorb the organic solvent or separate first solvent with At least second solvent；(d) element is recalled from the mixture and extract the organic solvent or the first solvent from the element；And And (e) reuse the element.

A kind of heat management device is additionally provided, contains foam derived from humic acid as thermal diffusion or heat-dissipation member. The heat management device can contain the device selected from the following terms: heat exchanger, radiator, heat pipe, high conductance plug-in unit, radiator Conductibility plate, thermal diffusion component, dissipation of heat component, hot interfacial medium or thermoelectricity or Peltier (Peltier) between heat source Cooling device.

Detailed description of the invention

Fig. 1 shows the schematic diagram for the method from natural graphite particles production graphene film.

The possible mechanism for being connected chemically and merging between Fig. 2 humic acid molecule between " the HA molecule of connection ".Two A or three original HA molecules can be coupled chemically together to form longer or broader HA molecule, be referred to as " connection HA molecule ".Multiple " the HA molecules of connection " can merge to form graphene-like lonsdaleite atomic plane.

Foam derived from the HA that Fig. 3 (A) is produced by the method for the invention, graphite foam and Ni derived from mesophase pitch The heat conductivity value of the CVD grapheme foam of foam formwork auxiliary is relative to specific gravity；

The heat of foam derived from Fig. 3 (B) HA, the GO foam for sacrificing plastic bead template and hydrothermal reduction GO grapheme foam Conductivity value.

The conductivity data of foam and hydrothermal reduction GO grapheme foam derived from the HA that Fig. 4 is produced as the method for the present invention.

The heat conductivity value that Fig. 5 is drawn derived from the function as specific gravity of HA and the foam sample for being fluorinated HA.

The heat of the function as final (maximum) heat treatment temperature of foam sample of the Fig. 6 derived from HA and raw graphite alkene Conductivity value.

The oil mass that foam derived from every gram of HA of Fig. 7 is absorbed is as the oxygen in the foam with about 98% porosity level The function of content is drawn (from oil-aqueous mixtures separation oil).

The oil mass that foam derived from every gram of integral type HA of Fig. 8 is absorbed, the function as porosity level are drawn (it is assumed that oxygen Content is identical).

Fig. 9 absorbs chloroform amount out from chloroform-aqueous mixtures, and the function as degree of fluorination is drawn.

The schematic diagram (2 examples) of Figure 10 heat spreader structures.

Specific embodiment

Humic acid (HA) is typically found in the organic substance in soil, and alkali (such as KOH) can be used from soil Middle extraction.HA can also be extracted from a type of coal for being known as leonardite, which is the high oxidation of lignite Pattern.The HA extracted from leonardite, which contains, is largely located at the graphene-like molecular center (SP of lonsdaleite structure²Core) The oxygen-containing group (such as carboxylic group) of perimeter.The graphite oxide of this material and the strong acid oxidation production by natural graphite Alkene (GO) is slightly similar.HA have typical by weight 5% to 42% 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 with lower section (source: Stevenson F.J. " Humus Chemistry:Genesis, Composition, Reactions is provided in case 1 [humus chemistry: origin, composition, reaction], " John Wei Li father and son publishing company (John Wiley&Sons), New York 1994).

(scheme 1)

The non-aqueous solvent of humic acid include polyethylene glycol, ethylene glycol, propylene glycol, alcohol, sugar alcohol, polyglycereol, glycol ether, Solvent, the solvent based on amide, alkylene carbonates, organic acid or inorganic acid amine-based.

The present invention provides foams derived from a kind of humic acid being made of multiple holes and hole wall and its production method.Foam In hole be typically connected chemically/merge at a temperature of from 100 DEG C DEG C to 1,500 DEG C DEG C in sheet humic acid molecule (1) Together (edge-to-edge and/or face-to-face), and/or (2) are at (typically > 2,100 DEG C DEG C and more typically > 2,500 DEG C of high temperature DEG C) under along hole wall form biggish graphite crystal or domain (being referred to herein as being graphitized) during or later formed.

The present invention also provides a kind of production methods comprising: (a) preparation has the multiple corruption of dispersion in liquid medium The humic acid dispersion of acid molecule or piece is grown, wherein the humic acid selects autoxidizable humic acid, the humic acid of reduction, fluorinated corruption Grow acid, the humic acid of chlorination, brominated humic acid, the humic acid of iodate, the humic acid of hydrogenation, nitridation humic acid, doping Humic acid, chemical functionalization humic acid, or combinations thereof, and wherein the dispersion contains optional foaming agent, has from 0/ 1.0 to 1.0/1.0 foaming agent and humic acid weight ratio；(b) the graphene dispersion body is distributed and is deposited to supporting base material (example Such as plastic foil, sheet rubber, metal foil, sheet glass, the scraps of paper) surface on to form web rot grow acid layer；(c) from the wet humic acid Part or the liquid medium is completely removed in layer, to form dry humic acid layer；And (d) from 80 DEG C DEG C to 3,200 DEG C DEG C The first heat treatment temperature under be enough from non-carbon element (such as O, H, N, B, F, Cl, Br, I etc.) cause escaping gas molecule Or the desired rate of heat addition of Activation of blowing agent is heat-treated the drying humic acid layer to produce foam derived from humic acid.It is preferred that Ground, the distribution and deposition procedure include that the humic acid dispersion is made to be subjected to orientation induced stress.It is removed when being decomposed via thermal induction When, these non-carbon elements generate the escaping gas for serving as foaming agent or foaming agent.

Foam derived from resulting humic acid typically has from 0.005g/cm³To 1.7g/cm³(more typically from 0.01g/cm³To 1.5g/cm³And even more typically from 0.1g/cm³To 1.0g/cm³And most typically from 0.2g/cm³ To 0.75g/cm³) density, or from 50m²/ g to 3,000m²/ g is (more typically from 200m²/ g to 2,000m²/ g and most Typically from 500m²/ g to 1,500m²/ g) specific surface area.

Foaming agent or foaming agent be can via bubbling process in a variety of materials, (it undergoes hardening or phase transition, such as poly- Close object (plastics and rubber), glass and metal) in generate the substance of abscess or foaming structure.They are typically foamy Material applies when being in liquid.Having no knowledge about foaming agent before can be used for generating foamed material (when in solid-state).It is more significant Ground previously not yet teaches or implies that the aggregation of humic acid molecule can be converted into graphene-like foam via foaming agent.In order to The purpose for reducing density while increasing the thickness and relative rigidity of original polymer, increasing thermal resistance and sound insulation, typical real estate Foam structure in raw matrix.

For generating hole or abscess (bubble) in matrix with generate foam or cellular material foaming agent or relevant Bubble mechanism can be classified as with the following group:

(a) physical blowing agent: for example, hydrocarbon (for example, pentane, isopentane, pentamethylene), chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC) and liquid CO₂.Generate bubbles/foam process be heat absorption, i.e., it need heat (such as from melting process or by The chemical exothermal caused by being crosslinked) so that liquid blowing agent volatilizees.

(b) chemical foaming agent: for example, isocyanates, azo-based, hydrazine and other nitrogen material (be used for thermoplasticity and bullet Elastomeric foam), sodium bicarbonate (for example, sodium bicarbonate, is used for thermoplastic foam).Here, gaseous products and other by-products are logical It crosses chemical reaction to be formed, be promoted by the heat release heat of process or reaction polymer.Hair is served as since foamable reaction is related to being formed The low molecular weight compound of gas is steeped, therefore also discharges additional heat release heat.By powdered hydrogenated titanium metal foam production It is used as foaming agent in life, because it is decomposed to form titanium and hydrogen at elevated temperatures.In order to which identical purpose uses zircoium hydride (II).Once being formed, then low molecular weight compound will never revert to one or more original foaming agents, i.e., reaction is not Reversible.

(c) the physical/chemical foaming agent mixed: for example for producing the flexible polyurethane (PU) with low-down density Foam.Both chemical blowing and physical blowing can use in tandem, to put down each other relative to release/absorption thermal energy Weighing apparatus；Temperature is minimized as a result, to rise.For example, by isocyanates and water, (it is reacted to form CO₂) and liquid CO₂(its boil with Provide gaseous form) combine the flexible PU foam for being used for producing the very low-density for mattress.

(d) mechanical injection agent: the foam of machine-building is related to bubble introducing liquid polymerisable matrix (such as in liquid glue The uncured elastomer of newborn form) in method.Method be included in low viscosity latex stir into air or other gases or Low boiling point volatile liquid is injected a gas into extruder barrel or die head or is injected in injection-molded machine barrel or nozzle, and The sheared/mixed of screw rod is allowed to act on, so that gas is evenly dispersed to form very tiny bubble or gas in the melt Solution.When the melt is molded or extruded and component is in atmospheric pressure at present, gas comes out from solution, to make polymer Melt expands immediately before curing.

(e) soluble and can leaching agent: soluble filler, such as solid chlorine sodium crystal is mixed into Liquid amino formic acid In ester system, it is then shaped to solid polymer component, is immersed in the water more persistently later by by solid moulding part Time washes off the sodium chloride, to leave small interconnection hole in the polymeric articles of relative high density.

(f) we have found that, when HA derived material is in solid-state, above five kinds of mechanism may be used in these HA Hole is generated in derived material.It is by non-via those are removed in the high temperature environment that another mechanism in hole is generated in HA material Carbon generates and evaporating volatile gas.This is unique from bubbling process, is never taught or was suggested before.

Hole wall (cell wall) in foam of the invention is flat containing chemical bonding and combined graphene-like lonsdaleite atom Face.The aromatic molecules of these planes or the carbon atom of hexagonal structure physically and chemically interconnect well.These planes Lateral dimension (length or width) is huge (from 20nm to > 10 μm), typically compared with the maximum length of beginning humic acid molecule/ The big several times of width or even a number of orders of magnitude.Lonsdaleite atomic plane is substantially interconnected to form the long electronics with lower resistance Conduction path.This is not to be found, develop or suggest in the past a kind of unique and new material that may be present.

In step (b), preferably under the influence of shear stress, HA suspension is in solid substrate surface (such as PET film Or glass) on be formed as wet layer.One example of this shearing program is the thin of HA suspension of being cast or coated using coating machine Film.This program, which is similar on solid substrate, coats one layer of varnish, paint, coating or ink.When shaping membrane, or when roller/ Blade/between wiper and supporting base material is there are when the relative motion of sufficiently high speed of related movement, the roller, " scraper knife Piece " or wiper can produce shear stress.Quite unexpectedly with significant, this shear action makes plane HA points Son can be aligned well along such as shear direction.Further it was unexpectedly determined that the liquid in HA suspension ought be removed then Component with formed the height being at least partially dried alignment sheet HA molecule good stack layer when, do not destroy this molecular alignments State or preferred orientation.Dry HA film is in direction in face and perpendicular to having high birefringence coefficient between in-plane.

In one embodiment, this HA layers is then made to remove with Activation of blowing agent and/or from HA molecule through heat-treated Non-carbon element (such as F, O etc.) is reacted using the thermal induction for generating escaping gas as by-product.These escaping gas are solid Body HA material internal generates hole or bubble, sheet HA molecule is pushed into wall construction, to form HA foam.If not adding hair Infusion, then the non-carbon element in HA material preferably comprise from HA material by weight at least 10% (preferably at least 20%, and Further preferably at least 30%).First (initial) heat treatment temperature be typically greater than 80 DEG C DEG C, preferably greater than 100 DEG C DEG C, More preferably greater than 300 DEG C DEG C, be even more preferably greater than and 500 DEG C DEG C and 1,500 DEG C DEG C can be up to.Foaming agent typically exists It is activated at a temperature of 80 DEG C DEG C to 300 DEG C DEG C (but can be higher).Blistering program (formation in hole, abscess or bubble) is typical It is completed within the temperature range of 80 DEG C DEG C -1,500 DEG C DEG C on ground.Quite it was unexpectedly determined that with side between lonsdaleite atomic plane Being connected chemically or merging for opposite side and face-to-face mode (Fig. 2) can be in relatively low heat treatment temperature (for example, down to from 150 DEG C DEG C to 300 DEG C DEG C) under occur.

Foam derived from HA can be made to be subjected to further being heat-treated, which refers at least to be significantly higher than at the first heat Manage the second temperature of temperature.

Suitably programmed heat treatment process can be related to only single heat treatment temperature (for example, only the first heat treatment Temperature), (the first constant temperature for a period of time and is then raised to second temperature and is maintained at this at least two heat treatment temperatures Continue another a period of time under second temperature), or be related to initial processing temperature (the first temperature) and final HTT (second) and (be higher than the One temperature) heat treatment temperature (HTT) any other combination.The highest of dry HA layers of experience or final HTT are segmented into four A different HTT scheme:

Scheme 1 (80 DEG C to 300 DEG C DEG C): (it is connected chemically and heat-treats scheme, and there are also foam in this temperature range The activation protocol of agent, if present), HA layers are mainly undergone the thermal induction of adjacent HA molecule to be connected chemically, such as the top of Fig. 2 It is schematically shown in point.This further relates to remove some non-carbon, such as O and H, so as to cause oxygen content from typically 20%-42% (O in HA) is to the reduction of about 10%-25%.This processing causes the interplanar spacing in foam wall from about 0.6-1.2nm (as former state dry) is reduced to about 0.4-0.6nm, and thermal conductivity increase to per unit specific gravity 100W/mK and/or Conductivity increases to per unit specific gravity 2,000S/cm.(because can change porosity level, and it therefore can change graphite The specific gravity of alkene foamed material, and when assuming that grapheme material is identical, both thermal conductivity and conductivity value change with specific gravity, These characteristic values must be divided by specific gravity, relatively in order to justice.Even if) in the case where this temperature range, can also it occur Some between HA molecule are connected chemically.Interplanar spacing keeps relatively large (0.4nm or bigger).Function of many containing O Group remains (such as-OH and-COOH).

Scheme 2 (300 DEG C DEG C -1,500 DEG C DEG C): being connected chemically herein and adjacent HA molecule or company in Merge Scenarios, occurs Extensive chemical combination, polymerization and crosslinking between the HA molecule connect, to form starting graphite alkene shape lonsdaleite atomic plane, such as Shown in the lower part of Fig. 2.Oxygen content is reduced to typically from 2% to 10% (for example, after being connected chemically and merging), from And interplanar spacing is caused to be reduced to about 0.345nm.This means that some starting graphiteizations are at such lower temperatures Start, and typically need up to 2, (what is be such as carbonized is poly- to start the graphitizable material of graphited routine for 500 DEG C of temperature Acid imide film) form sharp contrast.This is another different characteristic of grapheme foam and its production method of the invention.These Being connected chemically reaction leads to that thermal conductivity increases to per unit specific gravity > 250W/mK and/or conductivity increases to per unit specific gravity 2, 500-4,000S/cm。

Scheme 3 (1,500 DEG C DEG C -2,500 DEG C DEG C): herein orderly and in graphitization scheme, extensive graphitization has occurred Or graphene-like plane merges, and significantly improves so as to cause the structurally ordered degree in foam wall.As a result, oxygen content is reduced to Spacing is reduced to about 0.337nm (to depend on actual HTT and duration, in fact between typically 0.1%-2% and graphene Now from the degree of graphitization of 1% to about 80%).The improved degree of order also passes through thermal conductivity and increases to per unit specific gravity > 350W/ MK and/or conductivity increase to per unit specific gravity > 3,500S/cm to reflect.

Scheme 4 (be higher than 2,500 DEG C DEG C): herein in recrystallization and integrity scheme, crystal boundary and other defect has occurred A large amount of mobile and elimination, so as to cause the almost ideal monocrystalline or polycrystalline graphite with huge crystal grain is formed in foam wall Alkene shape crystal, can the orders of magnitude more several greatly than the original size of HA molecule.Substantially eliminate oxygen content, typically 0%- 0.01%.Interplanar spacing is reduced to about 0.3354nm (degree of graphitization is from 80% to close to 100%), corresponds to perfect graphite The interplanar spacing of monocrystalline.The foaming structure so obtained shows per unit specific gravity > 400W/mK thermal conductivity and per unit Specific gravity > 4,000S/cm conductivity.

Foaming structure derived from HA of the invention can by at least cover first scheme (typically if temperature never More than 500 DEG C, then 1-4 hours are needed in this temperature range), more generally cover first two scheme (1-2 hour preferably), Even more typically first three scheme (the 0.5-2.0 hour preferably in scheme 3) and can cover all 4 kinds of schemes (packet Include scheme 4 and continue 0.2 to 1 hour, can be carried out to realize highest conductivity) the dry HA of temperature program(me) heat treatment come It obtains.

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 type crystals interlayer spacing in terms of nm.Only work as d₀₀₂Equal to or less than about 0.3440nm When, this equation is just effective.With the d for being higher than 0.3440nm₀₀₂HA derived from foam wall reflect it is flat to increase as interval base The presence of the oxygen-containing functional group (such as graphene-like planes of molecules surface or-OH, > O and-COOH on edge) of spacing between face.

Six sides in the foam wall and ordinary graphite crystal of graphene-like derived from HA stacking and being bonded can be used to characterize Another structure index of the degree of order of carbon atom plane is " inlaying the latitude of emulsion ", the rocking curve reflected by (002) or (004) The full width at half maximum (FWHM) of (X-ray diffraction intensity) indicates.This degree of order characterization graphite or graphene crystalline size (or crystallite dimension), The amount and preferred degree of grain alignment of crystal boundary and other defect.The almost ideal monocrystalline of graphite is characterized by having 0.2-0.4's inlays latitude of emulsion value.Our graphene wall it is most of have inlay the latitude of emulsion value in the range of this 0.2-0.4 (if being produced with the heat treatment temperature (HTT) not less than 2,500 DEG C).However, if HTT 1,500 DEG C with 2,500 DEG C it Between, then some values are in the range of 0.4-0.7；And if HTT between 300 DEG C and 1,500 DEG C, then some values are in 0.7- In the range of 1.0.

It is illustrated in fig. 2 be it is plausible be connected chemically and merge mechanism, wherein as example illustrate only 2 alignment HA molecule fragment, although a large amount of HA molecule can be connected chemically together and it is multiple " the HA molecule of connection) can chemistry close And to form foam wall.In addition, be connected chemically to occur face-to-face, rather than just edge-to-edge for HA molecule or piece. These connection and merge reaction carries out in this way so that molecule by chemistry merge, connection and integrally turn to one it is single Entity.The simple aggregation body of the not single HA piece of resulting product, single entities, the single entities substantially have The substantially network of the interconnection giant molecule of infinite molecular weight.All composition lonsdaleite planes are in lateral dimension (length and width) On be very big, and if HTT sufficiently high (such as > 1,500 DEG C or much higher), then these planes are substantially mutually bonded Together.

Referred to using the combined further investigation of SEM, TEM, selected diffraction, X-ray diffraction, AFM, Raman spectroscopy and FTIR Show that (wherein length/width is typically > > 20nm, more allusion quotation to foam wall derived from HA by several huge lonsdaleite atomic planes Type > > 100nm, usually > > 1 μm, and in many cases > > 10 μm, or even > > 100 μm) constitute.If at final heat It manages temperature and is lower than 2,500 DEG C, then these huge graphene-like planes are usually not only by Van der Waals force (such as in conventional graphite In crystallite like that) but also by covalent bond stacks and be bonded along thickness direction (crystallography c- axis direction).In these situations Under, it is desirable to without being limited by theory, but Raman and FTIR spectrum method research seem to indicate sp²(leading) and sp³(weak but presence) electricity Sub- configuration coexists, rather than just the conventional sp in graphite²。

(1) graphite foam wall derived from this HA is not by will be discrete thin with resinoid bond, bridging agent or adhesive Piece/platelet gluing is bonded together manufactured.On the contrary, HA molecule is merged into a single whole by being connected with each other or being formed covalent bond Graphite alkene shape crystal entity, without the use of any external bridging agent added or bonding agent molecule or polymer.

(2) foam wall is typically the polycrystalline being made of the big crystal grain with imperfect crystal boundary.This entity is derived from more A HA molecule, and these aromatics HA molecule has lost its primary characteristic.From in suspension remove liquid component after, gained HA molecule forms substantially unbodied structure.In heat treatment, these HA molecular chemistries merge and connect into composition foam wall Single or monoblock type graphite bodies.This foam wall is high-sequential.

(3) since these unique chemical compositions (including oxygen content or non-carbon content), form, crystal structure are (including flat Spacing between face) and structure feature (such as the chemical bonding between high-orientation, few defects, imperfect crystal boundary, graphene film With it is very close to each other and do not interrupt substantially in lonsdaleite plane), foam derived from HA has outstanding thermal conductivity, conductance The unique combination of rate, mechanical strength and rigidity (elasticity modulus).

It is further noted that if non-carbon element content (H and O) is by weight from 2% to 20%, it can be to The hole wall of foam derived from humic acid assigns a certain desired hydrophilicity.These features make it possible to by from oil-water Oil is separated from water by selectively absorbing oily in mixture.In other words, foamed material derived from this HA can be recycled from water Oil, to help clean up oil spilling river, lake or ocean.Oily absorptive capacity is typically foam own wt from 50% To 500%.This is very useful material for environmental protection purpose.

If it is desired to which high conductivity or thermal conductivity, then can be such that HA- carbon foam is subjected at a temperature of being higher than 2,500 DEG C Graphitization processing.Resulting materials are particularly useful in thermal management applications (such as manufacturing fin radiator, heat exchanger or thermal expansion Dissipate device).

It is noted that HA- carbon foam can be made during graphitization processing and/or later through compressed.This operation It allows us to adjust graphene film orientation and porosity.

In order to characterize generation graphite material structure, obtain X-ray with the X-ray diffractometer that radiates equipped with CuKcv Diffraction pattern.The displacement of diffraction maximum and broadening use silicon powder reference substance are calibrated.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 when d₀₀₂When equal to or less than about 0.3440nm, this equation is just effective.In present invention research, there is the d higher than 0.3440nm₀₀₂ Graphene-like (HA or RHA) foam wall reflect as interval base to increase the oxygen-containing functional group of spacing between graphene (such as Graphene molecules plane surface or-OH, > O and-COOH on edge) presence.

The degree of order for the RHA plane in the foam wall and ordinary graphite crystal of graphene stacking and being bonded can be used to characterize Another structure index be " inlaying the latitude of emulsion ", by the rocking curve (X-ray diffraction intensity) of (002) or (004) reflection Full width at half maximum (FWHM) indicates.This degree of order characterization graphite or graphene crystalline size (or crystallite dimension), crystal boundary and other defect Amount and preferred degree of grain alignment.The almost ideal monocrystalline of graphite is characterized by having that 0.2-0.4's inlays the latitude of emulsion Value.Our RHA wall it is most of have inlay latitude of emulsion value (if with being not less than 2,500 DEG C in the range of this 0.2-0.4 Heat treatment temperature (HTT) produce).However, then some values are in 0.4-0.7 if HTT is between 1,500 DEG C and 2,500 DEG C In the range of；And if HTT between 300 DEG C and 1,500 DEG C, then some values are in the range of 0.7-1.0.

Referred to using the combined further investigation of SEM, TEM, selected diffraction, X-ray diffraction, AFM, Raman spectroscopy and FTIR Show humic acid-carbon foam wall by several big graphene planes (wherein length/width is typically > > 20nm, more typically > > 100nm, usually > > 1 μm, and in many cases > > 10 μm) constitute.This is quite unexpected, because carrying out heat Before processing, the lateral dimension (length and width) of original humic acid piece or molecule is typically < 20nm, and more typically <10nm.This hint, multiple HA pieces or molecule can edge-to-edge be merged into bigger (longer or wider) each other by covalent bond Piece.

If final heat treatment temperature is lower than 2,500 DEG C, then these big graphene-like planes usually can also not only lead to Cross Van der Waals force (as in conventional graphite microcrystal) but also by covalent bond along thickness direction (the axis side crystallography c- To) stack and be bonded.In these cases, it is desirable to which without being limited by theory, but Raman and FTIR spectrum method research seem to indicate sp²(leading) and sp³(weak but presence) electron configuration coexists, rather than just the conventional sp in graphite²。

Foam derived from integral type HA is made of multiple holes and hole wall, and middle hole wall contains the single layer being chemically bound together Or few layer HA piece, the HA plane that the graphene-like that wherein there is these few layer HA pieces 2-10 layer heap to fold merges, these planes have Such as pass through the interplanar spacing d of the slave 0.3354nm to 0.36nm of X-ray diffraction measurement₀₀₂, and single layer or few layer graphene-like HA piece contains by weight 0.01% to 25% non-carbon element (more typically < 15%).

Foam derived from integral type HA typically has from 0.001g/cm³To 1.7g/cm³Density, from 50m²/ g to 3, 000m²Specific surface area, per unit the specific gravity at least thermal conductivity of 200W/mK, and/or per unit specific gravity of/g is not less than 2,000S/ The conductivity of cm.In a preferred embodiment, these hole walls contain the graphene-like RHA plane of stacking, these graphenes Shape RHA plane has the interplanar spacing d such as the slave 0.3354nm to 0.40nm by X-ray diffraction measurement₀₀₂。

Many HA pieces can edge-to-edge be integrally combined formula reduction HA (RHA) entity each other by covalent bond.Due to these Unique chemical composition (including oxygen or hydrogen content etc.), form, crystal structure (including interplanar spacing) and structure feature (example As between the degree of orientation, few defects, graphene-like piece chemical bonding and it is very close to each other and along six side's in-planes substantially Do not interrupt), foam derived from HA has unique group of outstanding thermal conductivity, conductivity, mechanical strength and rigidity (elasticity modulus) It closes.

Thermal management applications

Features described above and characteristic make foam derived from integral type HA be for various engineering application and biomedical applications Ideal element.For example, the foam can be used in applying below merely for heat management purpose:

A) foam derived from compressible and HA with high heat conductance is preferably suited as thermal interfacial material (TIM), should Thermal interfacial material can be implemented between heat source and heat diffuser or between heat source and radiator.

B) foam derived from HA may be used as heat diffuser due to its high heat conductance in itself.

C) foam derived from HA is since (exhibiting high surface hole lures for its high heat diffusion capabilities (high heat conductance) and high heat-dissipation ability Lead large quantity of air convection current micron or nanochannel) and may be used as radiator or dissipation of heat material.

D) light weight is (in 0.001g/cm³With 1.8g/cm³Between adjustable low-density), per unit specific gravity or per unit The high heat conductance of phsyical density and high structural intergrity (HA piece is merged to form long electronics conduction path) make this Foam derived from HA is the ideal material for durable heat exchanger.

Heat management or dissipation of heat device based on foam derived from HA include heat exchanger, radiator (such as wing formula heat dissipation Device), heat pipe, high conductance plug-in unit, thin or thick conductibility plate (between radiator and heat source), hot interfacial medium (or hot interface Material, TIM), thermoelectricity or Peltier coldplate etc..

Heat exchanger is the device for transmitting heat between one or more fluids；For example, being separated in different channels The gas and liquid of flowing.These fluids are separated typically via solid wall to prevent from mixing.Foam derived from HA of the invention Material is the ideal material for this wall, and precondition is that the foam is not the complete open celled foam for allowing fluid to mix.This The method of invention makes it possible to produce both aperture and closed-cell foam structure.High surface pore area makes two or more fluids Between heat exchange it is significant faster.

Heat exchanger be widely used in refrigeration system, air-conditioning unit, heater, power station, chemical plant, petrochemical plant, Oil plant, natural gas processing and sewage treatment.The known example of heat exchanger is seen in internal combustion engine, and wherein cycle engine is cold But agent flows through radiator coil, and dynamic by these coil pipes with Airflow, this cools down the coolant and heats the sky of entrance Gas.Solid wall (such as the solid wall for constituting radiator coil) is usually made of high thermal conductivity material such as Cu and Al.With more Foam derived from the HA of the invention of high heat conductance or more high-specific surface area is the excellent replacement of such as Cu and Al.

There are the commercially available heat exchangers of many types: shell and tube exchanger, plate heat exchanger, shell-and-plate heat exchange Device, adiabatic wheel heat exchanger (adiabatic wheel heat exchanger), plate-fin heat exchanger, pillow plate heat exchanger (pillow plate heat exchanger), fluid heat exchanger, waste heat recovery unit, dynamic scraped surface heat exchanger (dynamic scraped surface heat exchanger), phase-change heat-exchanger, direct contact heat transfer device and microchannel Heat exchanger.Each in the heat exchanger of these types can use the high thermal conductivity and ratio of exception of foamed material of the invention Surface area.

Foam derived from solid HA of the invention can be used in radiator.For dissipation of heat purpose, radiator is extensive For in electronic device.Centre in portable microelectronic device (such as laptop, tablet computer and smart phone) It manages unit (CPU) and battery is well known heat source.Typically, make metal or graphite object (such as Cu foil or graphite foil) and hotlist Face contact and this object help heat diffusion to outer surface or outside air is (main by conduction and convection current and smaller Pass through radiation in degree).In most cases, thin thermal interfacial material (TIM) heat source hot surface and heat diffuser or Mediation is played between the thermal diffusion surface of radiator.(foam derived from HA of the invention is also used as TIM.)

Radiator is usually made of high conductance material structure, which has one or more flat Surface to ensure to thermally contact with there is the good of component to be cooled, and have a series of pectinations or aliform protruding portion with increase with The surface of air contacts, and therefore increases rate of heat dispation.Radiator can be used with fan combination to increase the sky on radiator Flow of air rate.Radiator can have multiple fins (extension or surface outstanding) to improve heat transmitting.With finite quantity Space electronic device in, shape/arrangement of fin must be optimised, so that heat transmitting density maximizes.Alternatively or Additionally, cavity (being inverted fin) is embedded in the region that can be formed between adjacent fins.These cavitys are effective in by heat It is extracted in radiator from multiple heat main bodys.

Typically, integrated radiator includes heat collection component (core or base portion) and integral with the heat collection component (base portion) At least one dissipation of heat component (such as one or more fins) to form fin radiator.These fins and the core are natural Ground connection or integration become whole together, without use the external adhesive applied or mechanical fasteners device by these Fin is connected to the core.Thermal-arrest base portion has the surface thermally contacted with heat source (such as LED), collects heat from this heat source, and It is dissipated heat into air by these fins.

As illustrative example, Figure 10 provides the schematic diagram of two kinds of radiators: 300 and 302.The first contains thermal-arrest structure Part (or base component) 304 and the multiple fins or dissipation of heat component (such as fin 306) for being connected to the base component 304.It is aobvious Show that base component 304 has the heat collecting surface 314 for being intended to thermally contact with heat source.Display dissipation of heat component or fin 306 at least have There is heat dissipation surface 320.

Particularly useful embodiment is integral type radial direction radiator 302, which includes radial fin radiator component, The component includes: (a) base portion 308, which includes heat collecting surface 318；And (b) by the base portion 308 support or with the base The integral multiple parallel plane fin members (such as two examples 310,312) spaced apart in portion, wherein these are flat Face fin members (such as 310) include at least one heat dissipation surface 322.Multiple parallel plane fin members are preferably equidistant Spaced apart.

Foam itself derived from high flexibility of the invention and elastic HA is good thermal interfacial material and is also Highly effective thermal diffusion component.In addition, this high conductance foam is also used as electronic device cooling and for enhancing The plug-in unit of heat discharge from small chip to radiator.Because being to be primarily upon by the space that high conductance material occupies, more Efficient design is to utilize the high conductance path that can be embedded into heating element.Elasticity disclosed herein and highly conductive property are solid Body grapheme foam fully meets these requirements.

High resiliency and high-termal conductivity make foam derived from solid HA of the invention become good conductibility slab, the thickness Plate, which has, to be placed between heat source and cold flow fluid (or any other radiator) to be used as heat transfer interface to improve cooling performance. In this arrangement, cooling under heat source cystosepiment derived from thick HA, rather than directly contact with cooling fluid to cool down.HA spreads out The slab of raw foam can significantly improve the heat transmitting between heat source and cooling fluid by conducting hot-fluid in the best way. Other pump power and additional heat transfer surface area are not needed.

Foam derived from HA is also the outstanding material for constructing heat pipe.Heat pipe is the steaming using two-phase working fluid or coolant It sends out and condenses to transmit the heat-transfer arrangement of amount of heat, there are very small temperature differences between hot interface and cold interface. Conventional heat pipe is made of following item: sealing hollow tube made of heat-conducting metal such as Cu or Al；And make working fluid from steaming Hair device is back to the liquid-sucking core (wick) of condenser.Saturated liquid of the pipe containing working fluid (such as water, methanol or ammonia) and steaming Both gas, every other gas are excluded.However, both Cu and Al be easy to aoxidize or corrode, and therefore its performance with Time relatively quickly degrades.In contrast, foam derived from HA is chemically inert and does not have these oxidations or corrosion Problem.Heat pipe for electronic device heat management can have foam big envelope and liquid-sucking core, use water as working fluid.If Heat pipe needs to operate under the freezing point lower than water, and foam/methanol derived from HA can be used, and foam derived from HA/ammonia heat Pipe can be used for the electronic device cooling in space.

Peltier coldplate is worked based on Peltier effect by applying electric current connecing in two different electric conductors Heat flux is generated between chalaza.This effect is commonly used in cooling electronic component and small instrument.In practice, many this kind of junctions It can be with arranged in series the effect is increased to the required amount of being heated or cooled.Foam derived from HA can be used for improving hot biography Pass efficiency.

Filtering and fluid absorb application

Foam derived from HA can be made into the mesoscale containing microcosmic hole (< 2nm) or with the aperture from 2nm to 50nm Hole.Foam derived from HA can also be made into containing micron order hole (1-500 μm).It is based only upon the aperture well controlled, the present invention HA derived from foam can be for air or water filtering abnormal filtering material.

In addition, humic acid (HA) hole wall chemistry can be controlled to the functional group of not same amount and/or type being given to hole Wall (for example, as reflected by the percentage of O, F, N, H in foam).In other words, to the different positions in aperture and internal structure While both chemical functional group at point place or independent control offer in terms of designing and manufacturing foam derived from HA without precedent Flexibility or highest freedom degree, foam derived from these HA shows many unexpected characteristics, synergistic effect and usually It is considered certain unique combination of mutually exclusive characteristic (for example, certain a part of structure is hydrophobic and other parts It is hydrophilic；Or foaming structure is not only hydrophobicity but also lipophilic).If water is by material or exclusion, then it is assumed that this Kind surface or material are hydrophobic, and the water droplet being placed on hydrophobic surface or material will form big contact angle.If Surface or material have strong affinity for oil and do not have for water, then it is assumed that the surface or material are lipophilic.The present invention Method allows accurately to control hydrophobicity, hydrophily and lipophilicity.

The present invention also provides the devices of a kind of oil removing, separation oil or oil recovery, contain bubble derived from HA of the invention Foam is as the element for absorbing oil or separation oil.Additionally provide it is a kind of except solvent or separate the device of solvent, it is derivative to contain the HA Element of the foam as lyosoption.

Use foam derived from HA of the invention as the major advantage of element for absorbing oil be its structural intergrity.Due to HA piece chemistry merges and therefore with the viewpoint of high structural intergrity, and gained foam will not after duplicate absorption oil operation Disintegration.In contrast, it has been found that by hydrothermal reduction, vacuum assisted filtration or freeze-drying preparation based on graphene The element for absorbing oil can be disintegrated after absorbing oil 2 or 3 times.Only without anything (in addition to before with oily initial contact Existing weak Van der Waals force) graphene film of these separation originally is kept together.Once these graphene films are wetting by the oil, Then they are no longer able to restore to the original shape for the element for absorbing oil.

Another major advantage of the technology of the present invention be design and manufacture can absorb at most up to its own weight The oil of 400 times of amount but still the flexibility in terms of maintaining the element of the absorption oil of its planform (and without significant expansion).This amount Depending on the ratio pore volume of foam, this can mainly pass through the amount of starting vector polymer beads before the heat treatment than pore volume Ratio between HA molecule or the amount of piece controls.

The present invention also provides one kind from oil-aqueous mixtures (such as oil spilling water or from the waste water of oil-sand) separation/recovery The method of oil.Method includes the following steps: (a) provides the element for absorbing oil, which includes foam derived from integral type HA； (b) contact oil-aqueous mixtures with the element, which absorbs oil from the mixture；And this (c) is recalled from the mixture It absorbs the element of oil and extracts the oil from the element.Preferably, this method includes another step (d): reusing the element.

In addition, that the present invention provides one kind is organic molten for separating from solvent-water mixture or from multi-solvent mixture The method of agent.Method includes the following steps: (a) provides the element for absorbing organic solvent, which includes integral type HA derivative Foam；(b) multi-solvent of the element with organic solvent-aqueous mixtures or containing the first solvent and at least the second solvent is mixed Object contact；(c) this element is made from the mixture to absorb the organic solvent or from least second solvent absorption first solvent； And the element (d) is recalled from the mixture and extracts the organic solvent or the first solvent from the element.Preferably, this method Including another step (e): reusing the element of the lyosoption.

Following instance is for illustrating about some details for practicing optimal mode of the invention and should not be solved It is interpreted as limiting the scope of the invention.

Example 1: humic acid and reduction humic acid from leonardite

Can by by leonardite be dispersed in alkaline aqueous solution (pH 10) come with very high yield (75% In range) extracted humic acid from leonardite.Solution acidification is then set to cause humic acid powder precipitation.In an experiment, Contain 1M KOH (or NH with 300ml under magnetic stirring₄OH) the leonardite of the 3g of deionized water dissolving twice of solution.It will PH value is adjusted to 10.Then filtering solution is to remove any bulky grain or any residual impurity.Only containing HC or there will be foaming To form a series of films on the resulting humic acid dispersion cast to glass baseplate of agent, for subsequent heat treatment.

In some samples, just before casting, chemical foaming agent (hydrazo-dicarbonamide) is added to the suspension In.Then apply shear stress using doctor blade resulting suspension is cast on glass surface, so as to cause HA molecule Orientation.After removing liquid, resulting HA coating film has can be from about 10nm to 500 μm (preferably and typically from 1 μm to 50 μm) thickness of variation.

In order to manufacture HA foam sample, then make the HA coating film through heat-treated, these heat treatments typically relate to 80 Initial thermal reduction constant temperature 1-8 hours of DEG C -350 DEG C continue followed by under 1,500 DEG C -2,850 DEG C of second temperature Heat treatment in 0.5 to 5 hour.It may be noted that, it has been found that film sample is applied while being subjected to the first heat treatment Compression stress is vital.This compression stress seems to help to maintain the good contact between HA molecule or piece, makes in this way The chemistry that obtaining can occur while forming hole between HA molecule or piece merges and connects.In the feelings of no this compression stress Under condition, thermally treated film is typically excessively porous, orientation/positioning of the composition lonsdaleite atomic plane in middle hole wall It is excessively poor and cannot mutually chemistry merge and connection.As a result, the thermal conductivity of grapheme foam, conductivity and machinery are strong Degree is badly damaged.

Example 2: the method for various foaming agents and pore-forming (generating bubble)

In field of plastics processing, chemical foaming agent is mixed into the form of powder or pellet in plastic granule and in higher temperatures The lower dissolution of degree.Be specifically used for foaming agent dissolution a certain temperature on, generate gaseous reaction products (usually nitrogen or CO₂), serve as foaming agent.However, chemical foaming agent cannot be dissolved in grapheme material, the grapheme material be solid and It is not liquid.This in grapheme material for generating hole using chemical foaming agent or abscess proposes challenge.

After many experiments, it has been found that when the first heat treatment temperature is enough to activate foamable reaction, substantially anyization Learning foaming agent (such as with powder or pellet form) may be used to generate hole or bubble in dry graphene layer.Chemical blowing Agent (powder or pellet) can disperse that solid can be deposited in liquid medium to become the second component in the suspension To form wet layer in supporting base material.Then this wet HA material layer can be dried and be heat-treated to activate the chemical foaming agent.Changing After foaming agent is activated and generates bubble, resulting blistering HA structure is largely maintained (even if then right When the structure applies higher heat treatment temperature).In fact, this is quite unexpected.

Chemical blowing agent (CFA) can be the organic or inorganic compound that gas is discharged in thermal decomposition.CFA is typically used The high density foam in acquisition, and be often used together with physical blowing agent to obtain low density foam.CFA can classify For neither endothermic nor exothermic, this refers to the decomposition type that they undergo.Heat absorption types of absorbent energy and typically decompose when release Carbon dioxide and moisture are put, and heat release type releases energy and usually generates nitrogen when decomposing.It is discharged by heat release foaming agent Gas total gas yield and pressure be usually above absorb heat type total gas yield and pressure.Commonly known heat absorption CFA exists It is decomposed in 130 DEG C to 230 DEG C (266 °F -446 °F) ranges, and some more common heat release foaming agents are at about 200 DEG C (392 °F) Lower decomposition.However, can reduce the decomposition range of most of heat release CFA by adding certain compounds.The activation (decomposition) of CFA Temperature is fallen into our heat-treatment temperature range.The example of suitable chemical foaming agent include sodium bicarbonate (sodium bicarbonate), hydrazine, Hydrazides, azodicarbonamide (exothermic chemical foaming agent), nitroso compound are (for example, N, N- dinitroso pentamethylene four Amine), hydrazine derivate (for example, 4.4 '-oxygen bis- (benzene sulfonyl hydrazides) and hydrazo-dicarbonamide) and bicarbonate (such as bicarbonate Sodium).These are commercially available all in plastics industry.

In the production of foamed plastics, physical blowing agent metered modeling in foam extrusion or injection-molded bubbling process Expect in melt, or is supplied in one of precursor material during polyurethane froth.Do not know that physical blowing agent can be with before For generating hole in HA material, which is in solid-state (unfused).We have surprisingly been observed that physical blowing agent (for example, CO₂Or N₂) can be injected into before coating or being cast in supporting base material in HA suspension flow.Even if removing liquid When body medium (such as water and/or alcohol), this will also generate foaming structure.Dry grapheme material layer can be removed in liquid and with Hole or the bubble of controlled quatity are maintained in heat treatment process afterwards.

Technically feasible foaming agent includes carbon dioxide (CO₂), nitrogen (N₂), iso-butane (C₄H₁₀), pentamethylene (C₅H₁₀), isopentane (C₅H₁₂)、CFC-11(CFCI₃)、HCFC-22(CHF₂CI)、HCFC-142b(CF₂CICH₃) and HCFC- 134a(CH₂FCF₃).However, Environmental security is principal element in need of consideration when selecting foaming agent.Montreal Protocol And its influence to the agreement of consequentiality causes huge challenge to foam manufacturer.Although the chlorofluorocarbons applied in the past has Effective characteristic and tractability, but due to its ozone depletion potential (ODP), the whole world is all agreed to forbid these.Part halogen The chlorofluorocarbons of change is also not Environmental security, and therefore disabled in many countries.Substitute is hydrocarbon, such as iso-butane And pentane and gas, such as CO₂And nitrogen.

Other than those controlled substances, above-mentioned all foaming agents are tested in our experiment.Physics is sent out The foaming dosage being introduced into suspension is defined as the weight ratio of foaming agent Yu HA material by both infusion and chemical foaming agent, It is typically from 0/1.0 to 1.0/1.0.

Example 3: humic acid is prepared from coal

In an exemplary program, the coal of 300mg is suspended in the concentrated sulfuric acid (60ml) and nitric acid (20ml), and then Carry out cup ultrasonic treatment (cup sonication) 2h.Then it is stirred to react and is heated in oil bath at 100 DEG C or 120 DEG C 24h.The step of solution is cooled to room temperature and is poured into the beaker containing 100ml ice, is then added NaOH (3M), Until pH value reaches 7.

In an experiment, then neutral blends are filtered by 0.45-mm polytetrafluoroethylene film, and filtrate is existed It dialyses 5 days in 1,000Da bag filter.For biggish humic acid piece, the time 1h can will be foreshortened to using cross flow one ultrafiltration To 2h.After purifying, using rotary evaporation concentrate solution to obtain solid humic acid piece.By these individual humic acid pieces and The mixture of itself and foaming agent is redispersed in solvent (respectively, ethylene glycol and alcohol) to obtain several dispersion samples, with In subsequent casting or coating.

To chemical foaming agent (five Asia of N, N- dinitroso of not same amount (relative to HA material, by weight 1%-30%) Tetramine or 4.4 '-oxygen bis- (benzene sulfonyl hydrazides) are added in the suspension containing HA piece.Then it is cut using doctor blade application The suspension is cast on glass surface by shearing stress, so as to cause the orientation of HA molecule or piece and appropriate positioning.It casts several Kind sample, including using the CO being just introduced into before casting in suspension₂The manufactured sample as physical blowing agent.It is removing It goes after liquid, resulting HA film has the thickness that can change from about 1 μm to 100 μm.

Then make HA film through heat-treated, these heat treatments are related to 80 DEG C -1, and 500 DEG C initial (first) heat-treats temperature Continue 1-5 hours.This first heat treatment generates the big of HA foam (if HTT < 300 DEG C) and the lonsdaleite atomic plane in hole wall The foam (if HTT be from 300 DEG C to 1,500 DEG C) in sheet HA molecule or domain.Then make in foam sample it is some be subjected to 1, Whether 500 DEG C -2,850 DEG C of second temperature can be into one with the graphene-like domain for determining the lonsdaleite atomic plane in foam wall Walk perfect (graphitization is to become more orderly or with higher crystallinity).

CVD grapheme foam on comparison example 3-a:Ni foam formwork

The program is adapted from program disclosed in following discloses document: Chen, Z et al. " Three-dimensional flexible and conductive interconnected graphene networks grown by chemical Vapour deposition [graphene network is interconnected by the three-dimension flexible and conductibility of chemical vapor deposition growth] ", Nat.Mater. [nature material] 10,424-428 (2011).Select nickel foam (porous with 3D nickel bracket interconnected Structure) as grapheme foam growth template.In short, by decomposing CH at 1,000 DEG C under ambient pressure₄Carbon is drawn Enter in nickel foam, and then graphene film is deposited on the surface of nickel foam.Due to the thermal expansion between nickel and graphene The difference of coefficient forms ripple and wrinkle on graphene film.In order to recycle (separation) grapheme foam, it is necessary to etch away Ni frame Frame.Passing through hot HCl (or FeCl₃) before solution etches away nickel skeleton, poly- (metering system is deposited on the surface of graphene film Sour methyl esters) (PMMA) thin layer prevented in nickel etching process as supporter graphene network collapse.Small by hot acetone After the heart removes PMMA layers, frangible grapheme foam sample is obtained.The use of PMMA supporting layer is to preparing the only of grapheme foam Vertical film is crucial；In the case where no PMMA supporting layer, the grapheme foam sample of serious distortion and deformation is only obtained. This be not environment friendly and can not scale cumbersome technique.

Comparison example 3-b: the ordinary graphite foam from the carbon foam based on pitch

Asphalt powder, particle or spherolite are placed in the aluminum die with desired final foam shape.It uses Mitsubishi ARA-24 mesophase pitch.Sample is evacuated to less than 1 support and is then heated to about 300 DEG C of temperature.This When, vacuum is discharged into blanket of nitrogen and then applies the pressure of up to 1,000psi.Then the temperature of system is increased to 800℃.This is carried out with the rate of 2 DEG C/min.Temperature is kept at least 15 minutes to realize immersion and be then shut off furnace power supply And be cooled to room temperature with the rate of about 1.5 DEG C/min., it is released stress with the rate of about 2psi/min.Final foam temperature Degree is 630 DEG C and 800 DEG C.During cooling cycle, pressure is gradually released to atmospheric conditions.Then under a nitrogen blanket by foam It is heat-treated to 1050 DEG C and is then heat-treated to 2500 DEG C and 2800 in argon gas in a separate operation in graphite crucible ℃。

Sample machine from foam is machined for the sample of measurement thermal conductivity.The range of bulk thermal conductivities is from 67W/mK To 151W/mK.The density of sample is from 0.31-0.61g/cm³.When considering weight, the specific conductance of the foam of the pitch derived Rate is every specific gravity (or every phsyical density) about 67/0.31=216 and 151/0.61=247.5W/mK.

With 0.51g/cm³The compressive strength of sample of averag density to be measured as 3.6MPa and compression modulus tested Amount is 74MPa.In contrast, the compressive strength and pressure of graphite foam derived from the HA of the invention with comparable phsyical density Contracting modulus is 5.7MPa and 103MPa respectively.

Fig. 3 (A) shows the CVD of graphite foam derived from foam, mesophase pitch derived from HA and Ni foam formwork auxiliary The heat conductivity value relative to specific gravity of grapheme foam.These data clearly illustrate following unpredictable consequence:

1) assume that phsyical density is identical, the CVD stone assisted with graphite foam derived from mesophase pitch and Ni foam formwork Both black alkene is compared, and foam derived from the HA produced by the method for the invention shows significant higher thermal conductivity.

2) in view of following viewpoint, this is quite unexpected: CVD graphene is mainly never exposed to aoxidize and answer Derived from the raw graphite alkene for showing the much higher thermal conductivity compared with lonsdaleite atomic plane derived from HA, these HA Lonsdaleite atomic plane is the defective property of height after removing oxygen-containing functional group via conventional thermal reduction or chemical reduction method (with high defects count and therefore have low conductivity).It is observed using graphite foam derived from HA produced herein These abnormal high heat conductivity value let us it is very surprised.

3) assume that the amount of solid material is identical, foam derived from HA of the invention is after HTT > 1,500 DEG C of heat treatment Be inherently it is most conductive, which reflects high-caliber graphite crystal integrality (bigger crystalline sizes, less crystal boundary With other defect, better crystal orientation etc.).This is also unexpected.

4) the ratio conductance values of foam (Fig. 5) derived from foam and fluorinated HA derived from HA of the invention show every list Value of the position specific gravity from 250 to 490W/mK；But the ratio conductance values of other two kinds of foamed materials are typically that per unit specific gravity is lower than 250W/mK。

Comparison example 3-c: the preparation of raw graphite alkene foam (0% oxygen)

Recognize a possibility that high defects count is worked to reduce the conductivity of single graphene planes in HA piece, we Determine whether research can lead to have more high fever using raw graphite alkene piece (non-oxide and anaerobic, non-halogenated and halogen-free etc.) The grapheme foam of conductance.Raw graphite alkene piece is by using direct ultrasonic processing technique (being also referred to as liquid phase extruding) in this field To produce.

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.There is no other non-carbon elements.

To chemical foaming agent (N, the N- dinitroso of not same amount (relative to grapheme material, by weight 1%-30%) Pentamethylene tetramine or 4.4 '-oxygen bis- (benzene sulfonyl hydrazides) are added to the suspension containing raw graphite alkene piece and surfactant In.Then suspension is cast on glass surface.It casts several sample, including uses and be just introduced into suspension before casting CO in liquid₂The manufactured sample as physical blowing agent.After the liquid is removed, gained graphene film have can be from about 10 μm to 100 μm change thickness.Then make these graphene films be subjected to 80 DEG C -1,500 DEG C at a temperature of heat treatment continue 1-5 hours, generate grapheme foam.

A series of thermal conductivity number of foam derived from a series of foam derived from HA and raw graphite alkene is summarized in Fig. 6 According to the two is drawn relative to identical final (maximum) heat treatment temperature.These data indicate the thermal conductivity of foam derived from HA It is highly sensitive to final heat treatment temperature (HTT).Even if when HTT is very low, clearly the connection of certain form of HA molecule and Merge or crystal perfection reaction has been activated.Thermal conductivity is increased monotonically with final HTT.In contrast, raw graphite alkene steeps The thermal conductivity of foam keeps relative constant, until reaching about 2,500 DEG C of final HTT, shows the recrystallization of graphite crystal and complete The beginning of whole property.There is no functional group in raw graphite alkene ,-the COOH in such as HA and-OH, these functional groups make it possible to Chemical linker molecule under relatively low HTT.In the case where the HTT down to 1 250 DEG C, HA molecule and resulting lonsdaleite atom Plane can merge to form the significant bigger graphene-like that there is reduced crystal boundary and less electronic transmission path to interrupt Lonsdaleite piece.Although the derivative piece of HA is inherently more defective than raw graphite alkene, method of the invention enables HA molecule It is enough to form the graphite foam for being better than raw graphite alkene foam.This is another unpredictable consequence.

Comparison example 3-d: graphene oxide (GO) suspension is prepared from natural graphite and from the graphite oxide of hydrothermal reduction Alkene prepares grapheme foam

Graphite oxide be by 30 DEG C with the oxygen being made of the sulfuric acid, sodium nitrate and potassium permanganate of 4:1:0.05 ratio The preparation of agent liquid oxidation graphite flake.It is soaked in oxidant mixture liquid when by natural graphite flake (14 μm of partial sizes) When stain was with dispersion 48 hours, suspension or slurry present and keep optically opaque and dark.After 48 hours, by reactive material 3 times are rinsed with water adjusting pH value at least 3.0.Then the water of final quantity is added to prepare a series of GO- water slurries.It sees It observes when GO piece accounts for > 3% and typically from 5% to 15% weight fraction, GO piece forms liquid crystalline phase.

Then graphene hydrogel (SGH) sample of self assembly is prepared by hydro-thermal method.In typical program, SGH can With the uniform graphene oxide easily by heating the 2mg/mL being sealed in the autoclave of teflon liner at 180 DEG C (GO) prepared by water-borne dispersions 12h.SGH containing about 2.6% (by weight) graphene film and 97.4% water has about 5x 10^-3The conductivity of S/cm.At 1,500 DEG C after dry and heat treatment, resulting grapheme foam is shown about 1.5x10^-1The conductivity of S/cm, the conductivity are derivative by carrying out the HA of the invention of heat treatment production at the same temperature 2 times of conductivity of foam it is low.

Comparison example 3-e: the plastic bead template of the graphene oxide foam of reduction assists being formed

It is prepared for the hard template guidance for macropore blistering graphene film (MGF)

Ordered assemblies.Monodisperse polymethyl methacrylate (PMMA) latex spheres are used as hard template.It will compare above The GO liquid crystal prepared in example 3-d is mixed with PMMA ball suspending liquid.Then subsequent vacuum filter is carried out to prepare PMMA ball The component of body and GO piece, wherein GO piece is wrapped on PMMA pearl.Composite membrane is stripped down from filter, is air-dried and It is calcined at 800 DEG C to remove PMMA template and simultaneously heat-treat GO for RGO.Canescence stand alone type PMMA/GO film is after firing Blackening, and graphene film keeps porous.

Fig. 3 (B) shows foam derived from HA of the invention, steeps via the GO for sacrificing the production of plastic bead template householder method The heat conductivity value of the GO grapheme foam of foam and hydrothermal reduction.More surprisingly, it is assumed that HTT is identical, and HA of the invention is derivative Foam show highest thermal conductivity.The conductivity data summarized in Fig. 4 is also consistent with this conclusion.These data are further propped up Held following viewpoint: it is assumed that the amount of solid material is identical, HA suspension deposition (there is stress induced orientation) of the invention and Subsequent heat treatment generates foam derived from HA, foam derived from the HA be inherently it is most conductive, which reflects highests (bigger crystalline size, less crystal boundary and other defect takes along the better crystal of hole wall for horizontal graphite crystal integrality To etc.).

It is important to note that, whole art methods for producing graphite foam or grapheme foam seem to provide tool Have only in about 0.2g/cm³-0.6g/cm³In the range of phsyical density macrocellular foam, for most of intended application Aperture is typically too big (such as from 20 μm to 300 μm).In contrast, having the present invention provides generation can be down to 0.01g/ cm³And up to 1.7g/cm³Density HA derived from foam method.It aperture can be in mesoscale (2-50nm) to large scale Change between (1-500 μm), this depends on the content of non-carbon element and amount/type of foaming agent used.In design different type Graphite foam in terms of this flexibility and versatility level be that unexampled and any art methods can not be equal to.

Example 4: the preparation of fluorination HA foam

In exemplary program, foam piece derived from HA is fluorinated by chlorine trifluoride steam in sealing autoclave reactor, To generate fluorinated HA- carbon hybrid film.Allow the duration of different fluorination times to realize different degree of fluorination.Then by fluorine Foam derived from the HA of change is individually immersed in respectively containing in chloroform-aqueous mixtures container.It is observed that these foams Piece selectively absorbs chloroform from water and the amount of chloroform absorbed increases with degree of fluorination, until fluorine content reach by Poidometer 7.2%, as indicated in fig. 9.

Example 5: the preparation of nitridation HA foam

If foam derived from the dry plate HA prepared in example 3 is immersed 30%H₂O₂In aqueous solution continue 2-48 hours when Between section to obtain foam derived from oxidation HA, these foams have the controlled oxygen content of 2%-25% by weight.

Foam sample derived from some oxidation HA is mixed with the urea of different proportion, and these mixtures are anti-in microwave Answer heating 0.5 to 5 minute in device (900W).Product is washed with deionized several times and is dried in vacuo.Production obtained Object is nitridation HA foam.Nitrogen content is from 3% to 17.5 weight %, as measured by elemental analysis.

It is noted that the different functionalizations processing of foam derived from HA is for various purposes.For example, oxidation HA foam knot Structure is especially effectively as the absorbent of the oil from oil-aqueous mixtures (that is, oil is sprinkled upon waterborne and then mixes) , Fig. 7 and Fig. 8.In this case, foaming structure derived from integral type HA (having the oxygen of 0%-15% by weight) is both Hydrophobicity is again lipophilic (Fig. 7).If water is by material or exclusion, then it is assumed that this surface or material be it is hydrophobic, And the water droplet being placed on hydrophobic surface or material will form big contact angle.If surface or material have strong parent for oil Do not have with power for water, then it is assumed that the surface or material are lipophilic.

O, the different content of F, and/or N is but also foam derived from HA of the invention can absorb from water and different have Solvent separates a kind of organic solvent from the mixture of multi-solvents.

Example 6: the characterization of foam derived from various HA and ordinary graphite foam

Use the internal structure (crystal structure and orientation) of the HA- carbon foam of several series of X-ray diffraction studies.It The X-ray diffraction curve of right graphite typically shows the peak at about 2 θ=26 °, corresponds approximately to the graphite of 0.3345nm Spacing (d between alkene₀₀₂).The RHA wall of hybrid foam material shows typically from 0.3345nm to 0.40nm but more typically high Up to the d of 0.34nm₀₀₂Spacing.

2,750 DEG C of foaming structure of heat treatment temperature under compression is continued 1 it is small in the case of, d₀₀₂Spacing It is reduced to about 0.3354nm, it is identical as the spacing of graphite monocrystalline.In addition, having the second high-intensitive diffraction maximum corresponding to Occur from 2 θ=55 ° of the X-ray diffraction of (004) plane.(004) peak intensity on same diffraction curve relative to (002) intensity or I (004)/I (002) ratio, are the crystal perfection degree of graphene-like plane and the good finger of preferred orientation degree Show.For lower than all graphite materials being heat-treated at a temperature of 2,800 C, (004) peak be not present or it is relatively weak, I (004)/I (002) ratio < 0.1.Graphite material (such as the height-oriented pyrolysis being heat-treated at 3,000 DEG C -3,250 DEG C Graphite, HOPG) I (004)/I (002) ratio in the range of 0.2-0.5.In contrast, it is held with 2,750 DEG C of final HTT The grapheme foam of preparation in continuous one hour shows 0.78 I (004)/I (002) ratio and 0.21 and inlays latitude of emulsion value, instruction Hole wall is the actually perfect graphite monocrystalline (if preparing under compressive force) with good 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 some ranges having in this 0.3-0.6 when producing, in foam derived from our HA Interior inlays latitude of emulsion value.

Be important to note that, down to 500 DEG C of heat treatment temperatures be enough to make between lonsdaleite atomic plane along hole wall Spacing is lower than 0.4nm between mean level of the sea, becomes closer to spacing between the mean level of the sea of natural graphite or graphite monocrystalline.The method Advantage is following viewpoint: the coating of this HA suspension and heat treatment strategy are allowed us to plane HA molecular organization, orientation/right Together and chemistry is merged into unified structure, and all graphene-like lonsdaleite atomic planes are now bigger (aobvious on lateral dimension Write the length and width for being greater than original HA molecule).It is potentially connected chemically and merges mechanism and shown in Fig. 3.This generates different Normal thermal conductivity and conductivity value.

In short, we successfully developed it is a kind of absolutely new, novel, unexpected and visibly different Foam material of graphite and related methods of production derived from HA foam or HA.Such new foamed material chemical composition (oxygen, fluorine, With the % of other non-carbon elements), structure (crystal perfection, crystallite dimension, defects count etc.), crystal orientation, form, producer It is derivative that method and characteristic are fundamentally different from and are clearly distinguishable from graphite foam derived from mesophase pitch, CVD graphene Foam and the hydrothermal reduction from GO grapheme foam and sacrifice pearl template auxiliary RGO foam.By of the invention Thermal conductivity, conductivity, elasticity modulus and the bending strength that foamed material is shown are much higher than those of prior art foamed material.

Claims (40)

1. foam derived from a kind of humic acid is made of multiple holes and hole wall, wherein the hole wall contains single layer or few layer is rotten Grow lonsdaleite atomic plane or piece derived from acid, the lonsdaleite that there is 2-10 layer heap to fold for few layer lonsdaleite atomic plane or piece Atomic plane, the lonsdaleite atomic plane of the stacking have the slave 0.3354nm to 0.60nm as passed through X-ray diffraction measurement Interplanar spacing d₀₀₂, and the single layer or few layer lonsdaleite atomic plane contain by weight 0.01% to 25% it is non- Carbon, and wherein the humic acid is selected from the group consisting of: the humic of the humic acid of oxidation, reduction Sour, fluorinated humic acid, the humic acid of chlorination, brominated humic acid, the humic acid of iodate, the humic acid of hydrogenation, nitridation corruption Grow acid, doping humic acid, chemical functionalization humic acid, with and combinations thereof.

2. foam derived from humic acid as described in claim 1, wherein the foam has from 0.005g/cm³To 1.7g/ cm³Density, from 50m²/ g to 3,200m²The specific surface area of/g, the per unit specific gravity at least thermal conductivity of 100W/mK, and/or every Unit specific gravity is not less than the conductivity of 500S/cm.

3. foam derived from humic acid as described in claim 1, wherein the foam has from 0.01g/cm³To 1.5g/cm³ Density or average pore size from 2nm to 50nm.

4. foam derived from humic acid as described in claim 1, wherein the foam contain by weight 0.01% to Non-carbon element content in 20% range, and the non-carbon element includes selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen or boron Element.

5. foam derived from humic acid as described in claim 1, wherein the hole wall contains fluorination humic acid and the bubble Foam contains by weight from 0.01% to 25% fluorine content.

6. foam derived from humic acid as described in claim 1, wherein the hole wall contains oxidation humic acid and the bubble Foam contains by weight from 0.01% to 25% oxygen content.

7. foam derived from humic acid as described in claim 1, wherein the foam has from 200m²/ g to 3,000m²/g Specific surface area or from 0.1g/cm³To 1.2g/cm³Density.

8. foam derived from humic acid as described in claim 1, the foam be in from 100nm to 10cm thickness and It the continuous length roll film form of at least 2 meters of length and is produced by roll to roll.

9. foam derived from humic acid as described in claim 1, wherein the foam has the oxygen by weight less than 1% Content or non-carbon content, and the hole wall has the lonsdaleite atomic plane stacked, the per unit specific gravity at least heat of 200W/mK Conductance, and/or per unit specific gravity are not less than the conductivity of 1,000S/cm, and the lonsdaleite atomic plane of the stacking, which has, to be less than The interplanar spacing of 0.35nm.

10. hybrid foam derived from humic acid as described in claim 1, wherein the foam has to be less than by weight 0.01% oxygen content or non-carbon content, and the hole wall contains the lonsdaleite atomic plane of stacking, per unit specific gravity at least The thermal conductivity, and/or per unit specific gravity of 300W/mK is not less than the conductivity of 1,500S/cm, and the lonsdaleite atom of the stacking is flat Face has the interplanar spacing less than 0.34nm.

11. foam derived from humic acid as described in claim 1, wherein the foam has to be not more than by weight 0.01% oxygen content or non-carbon content, and the hole wall contains the lonsdaleite atomic plane of stacking, per unit specific gravity at least The thermal conductivity, and/or per unit specific gravity of 350W/mK is not less than the conductivity of 2,000S/cm, and the lonsdaleite atom of the stacking is flat Face has the interplanar spacing less than 0.336nm.

12. foam derived from humic acid as described in claim 1, wherein the foam has former containing the lonsdaleite stacked The hole of the conductivity of the thermal conductivity of sub- plane, per unit specific gravity greater than 400W/mK, and/or per unit specific gravity greater than 3,000S/cm Wall, the lonsdaleite atomic plane of the stacking have the interplanar spacing less than 0.336nm.

13. foam derived from humic acid as described in claim 1, wherein the hole wall contains with flat less than 0.337nm Between face the lonsdaleite atomic plane of the stacking of spacing and latitude of emulsion value is inlayed less than 1.0.

14. foam derived from humic acid as described in claim 1, wherein the hole wall contains interconnection lonsdaleite atomic plane 3D network.

15. foam derived from humic acid as described in claim 1, wherein the foam contains with the hole from 2nm to 50nm The mesoscale hole of diameter.

16. the device of a kind of oil removing or separation oil contains foam derived from humic acid as described in claim 1 as absorption The element of oil.

17. it is a kind of except solvent or separate solvent device, contain foam conduct derived from humic acid as described in claim 1 Lyosoption or the element for separating solvent.

18. a kind of method for separating oil with water, the described method comprises the following steps:

A. the element for absorbing oil is provided, the element for absorbing oil includes foam derived from humic acid as described in claim 1；

Contact oil-aqueous mixtures with the element, the element absorbs oil from the mixture；

C. the element is recalled from the mixture and extract the oil from the element；And

D. the element is reused.

19. a kind of method for the Separation of Organic from solvent-water mixture or from multi-solvent mixture, the method packet Include following steps:

A. the element for absorbing organic solvent or separating solvent is provided, the element includes that humic acid as described in claim 1 spreads out Raw foam；

B. make the element and organic solvent-aqueous mixtures or the multi-solvent mixture containing the first solvent and at least the second solvent Contact；

C. allow to make element to absorb the organic solvent or separation first solvent and described at least the from the mixture Two solvents；

D. the element is recalled from the mixture and extract the organic solvent or the first solvent from the element；And

E. the element is reused.

20. a kind of heat management device contains foam derived from humic acid as described in claim 1 and disappears as thermal diffusion or heat Dissipate element.

21. heat management device as claimed in claim 20, containing device selected from the group below, the group consisting of: Conductibility plate, thermal diffusion component, the dissipation of heat between heat exchanger, radiator, heat pipe, high conductance plug-in unit, radiator and heat source Component, hot interfacial medium and thermoelectricity or Peltier cooling device.

22. a kind of method for producing foam derived from humic acid, which comprises

(a) preparation has the humic acid dispersion for dispersing multiple humic acid molecules or piece in liquid medium, wherein the corruption It grows acid and is selected from the group consisting of: the humic acid of oxidation, the humic acid of reduction, fluorinated humic acid, chlorination Humic acid, brominated humic acid, the humic acid of iodate, the humic acid of hydrogenation, the humic acid of nitridation, the humic acid of doping, chemistry Functionalized humic acid, with and combinations thereof, and wherein the dispersion contain optional foaming agent, have from 0/1.0 to 1.0/1.0 foaming agent and humic acid weight ratio；

(b) the humic acid dispersion is distributed and is deposited on the surface of supporting base material and grow acid layer to form web rot；

(c) part in acid layer is grown from the web rot or completely remove the liquid medium, to form dry humic acid layer；And

(d) to be enough to cause escaping gas from the non-carbon element under the first heat treatment temperature from 80 DEG C to 3,200 DEG C The desired rate of heat addition of molecule or the activation foaming agent is heat-treated the dry humic acid layer to produce the humic acid Derivative foam, foam derived from the humic acid is made of multiple holes and hole wall, wherein the hole wall contains single layer or few layer Six sides that there is 2-10 layer heap to fold for lonsdaleite atomic plane or piece derived from humic acid, few layer lonsdaleite atomic plane or piece Carbon atom plane, the lonsdaleite atomic plane of the stacking have as the slave 0.3354nm by X-ray diffraction measurement to The interplanar spacing d of 0.60nm₀₀₂, and the single layer or few layer lonsdaleite atomic plane contain by weight 0.01% to 25% non-carbon element.

23. method as claimed in claim 22, wherein the distribution and deposition procedure are including passing through the humic acid dispersion By orientation induced stress.

24. method as claimed in claim 22 further includes steps of and is being higher than first heat treatment temperature It is heat-treated foam duration derived from the humic acid under second heat treatment temperature it is enough to obtain the wherein hole wall and contains stacking A period of time of the graphite foam of lonsdaleite atomic plane, the lonsdaleite atomic plane of the stacking have from 0.3354nm to The interplanar spacing d of 0.36nm₀₀₂Non-carbon element content by weight less than 2%.

25. method as claimed in claim 22, wherein the foaming agent is physical blowing agent, chemical foaming agent, its mixing Object, dissolution and leaching agent or the foaming agent being mechanically induced.

26. method as claimed in claim 22, the method is roll to roll, wherein the step (b) and (c) include by institute Supporting base material is stated from feed roller to be fed to crystallizing field, the humic acid dispersion continuously or intermittently deposited to the branch support group To be formed on, acid layer is grown in the web rot, the dry web rot grows acid layer to form the dry humic acid on the surface of material Layer and the dry humic acid layer being deposited in the supporting base material is collected on collecting drum.

27. method as claimed in claim 22, wherein first heat treatment temperature is 500 DEG C from 100 DEG C to 1.

28. method as claimed in claim 24, wherein second heat treatment temperature includes at least temperature selected from the group below, The group consisting of: (A) 300 DEG C -1,500 DEG C, 1,500 DEG C -2 of (B), 100 DEG C, and 2,100 DEG C -3,200 DEG C of (C).

29. method as claimed in claim 24, wherein second heat treatment temperature is included in 300 DEG C -1,500 DEG C of ranges Interior constant temperature at least 1 hour, and the then constant temperature within the scope of 1,500 DEG C -3,200 DEG C at least 1 hour.

30. method as claimed in claim 24, wherein the non-carbon element includes element selected from the group below, and the group is by following Items composition: oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen and boron.

31. method as claimed in claim 24, wherein described to be heat-treated the dry humic acid under the first heat treatment temperature The step of layer (d), carries out under compressive stress.

32. method as claimed in claim 22 further comprises the thickness for reducing the foam, aperture or porosity water Flat compression step.

33. method as claimed in claim 24, wherein the described first and/or second heat treatment temperature contains 300 DEG C -1, Temperature within the scope of 500 DEG C, and the foam is with the oxygen content or non-carbon content and hole wall less than 1%, the hole wall tool There are interplanar spacing, the per unit specific gravity at least thermal conductivity of 250W/mK, and/or per unit specific gravity less than 0.35nm to be not less than The conductivity of 2,500S/cm.

34. method as claimed in claim 24, wherein the described first and/or second heat treatment temperature contain 1,500 DEG C- Temperature within the scope of 2,100 DEG C, and the foam has the oxygen content or non-carbon content, hole wall less than 0.01%, the hole Wall has the interplanar spacing for being less than 0.34nm, per unit the specific gravity at least thermal conductivity of 300W/mK, and/or per unit specific gravity not Conductivity less than 3,000S/cm.

35. method as claimed in claim 24, wherein the described first and/or second heat treatment temperature contains greater than 2,100 DEG C Temperature, and the foam have no more than 0.001% oxygen content or non-carbon content, hole wall, the hole wall have is less than The interplanar spacing of 0.336nm, no more than 0.7 inlay latitude of emulsion value, per unit the specific gravity at least thermal conductivity of 350W/mK, and/or Per unit specific gravity is not less than the conductivity of 3,500S/cm.

36. method as claimed in claim 24, wherein the described first and/or second heat treatment temperature contains not less than 2,500 DEG C temperature, and the foam has containing the lonsdaleite plane stacked, no more than 0.4 inlays latitude of emulsion value, per unit ratio The hole wall of conductivity of the great thermal conductivity, and/or per unit specific gravity in 400W/mK greater than 4,000S/cm, the six of the stacking Square carbon plane has the interplanar spacing less than 0.336nm.

37. a kind of for producing the roll to roll of the continuous length piece of foam derived from the humic acid, which comprises

(a) preparation has the humic acid dispersion of the humic acid molecule of dispersion in liquid medium, wherein the dispersion contains Foaming agent；

(b) continuously or intermittently the humic acid dispersion is distributed and is deposited on the surface of supporting base material and grown with forming web rot Acid layer, wherein the supporting base material is the continuous film supplied from feed roller and collects on collecting drum；

(c) part in acid layer is grown from the web rot or completely remove the liquid medium, in a heating zone or multiple heating Dry humic acid layer is formed in area；And

(d) to be enough to activate the foaming agent in containing one of described heating zone of heating temperature from 80 DEG C to 500 DEG C The desired rate of heat addition is heat-treated the dry humic acid layer to produce foam derived from the humic acid, and the humic acid spreads out Raw foam is made of multiple holes and hole wall, is put down wherein the hole wall contains lonsdaleite atom derived from single layer or few layer humic acid The lonsdaleite atomic plane that there is 2-10 layer heap to fold for face or piece, few layer lonsdaleite atomic plane or piece, the six of the stacking Square carbon atom plane has the interplanar spacing d such as the slave 0.3354nm to 0.60nm by X-ray diffraction measurement₀₀₂, and institute It states single layer or by weight 0.01% to 25% non-carbon element is contained in layer lonsdaleite atomic plane less.

38. method as claimed in claim 22, wherein foam derived from the humic acid has from 0.005g/cm³To 1.7g/ cm³Density, from 50m²/ g to 3,200m²The specific surface area of/g, the per unit specific gravity at least thermal conductivity of 100W/mK, and/or every Unit specific gravity is not less than the conductivity of 500S/cm.

39. method as claimed in claim 24, wherein foam derived from the humic acid has from 0.005g/cm³To 1.7g/ cm³Density, from 50m²/ g to 3,200m²The specific surface area of/g, the per unit specific gravity at least thermal conductivity of 100W/mK, and/or every Unit specific gravity is not less than the conductivity of 500S/cm.

40. method as claimed in claim 37, wherein foam derived from the humic acid has from 0.005g/cm³To 1.7g/ cm³Density, from 50m²/ g to 3,200m²The specific surface area of/g, the per unit specific gravity at least thermal conductivity of 100W/mK, and/or every Unit specific gravity is not less than the conductivity of 500S/cm.