CN105060283A - Preparation method and application of graphene slurry - Google Patents
Preparation method and application of graphene slurry Download PDFInfo
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- CN105060283A CN105060283A CN201510474145.XA CN201510474145A CN105060283A CN 105060283 A CN105060283 A CN 105060283A CN 201510474145 A CN201510474145 A CN 201510474145A CN 105060283 A CN105060283 A CN 105060283A
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Abstract
The invention relates to the graphene technical field, and specifically discloses a preparation method and an application of a graphene slurry. The preparation method of the graphene slurry includes the following steps of preparation of a graphite intercalated compound, preparation of a graphite expansion body and preparation of the graphene slurry, wherein an intercalator is any one of nitric acid with the mass concentration of 65%-98%, a mixture of nitric acid with the mass concentration of 65%-98% and an organic acid, and a mixture of nitric acid with the mass concentration of 65%-98% and phosphoric acid with the mass concentration of 80%-98%. The preparation of the graphene slurry has no need of concentrated sulfuric acid as a reaction medium, and the prepared graphene slurry does not contain sulfur and has less layer number. The graphene slurry can greatly increase multiplying power capability and cycle performance of lithium ion batteries when used in the lithium ion batteries, and can overcome defects of a conventional sulfur-containing graphene material in anticorrosive coatings when used in a graphene anticorrosive coating. The preparation method of the graphene slurry provides a good route for production and application of sulfur-free graphene and is suitable for realizing industrialization.
Description
Technical field
The present invention relates to grapheme material technical field, particularly relate to a kind of preparation method and application without sulfur graphite alkene slurry.
Background technology
Grapheme material is prepared since Britain graceful Chester college professor in 2004 pacifies strong K sea nurse (AndreK.Geim) of moral etc., just there is the focus that the performances such as unique structure, excellent electricity, mechanics, optics, chemistry and calorifics become many people research because of it, and pacify moral strong K sea nurse (AndreK.Geim) and Constantine Nuo Woxiaoluofu two scientists also because having the contribution of initiative work and brilliance in two-dimensional graphene investigation of materials, jointly obtain 2010 years Nobel Prizes in physics.
At present, the preparation in enormous quantities of graphene powder material mainly adopts the preparation method of " from top to bottom ", wherein mainly contains redox and intercalation peels off two kinds of methods.Oxide-reduction method natural flake graphite and strong acid and Strong oxdiative thing is reacted to generate graphite oxide (GO), graphene oxide (mono-layer graphite oxide) is prepared into through ultrasonic or the dispersion of other High shear device, add the oxygen-containing functional group (as carboxyl, hydroxyl and epoxy group(ing)) that graphite oxide surface removed by reductive agent again, thus obtain Graphene.Oxidation reduction process is adopted to carry out the preparation of Graphene, preparation efficiency is higher, more easily carry out industrial amplification production, the obtained Graphene number of plies is also fewer, just production process more complicated, obtained grapheme material structure by destruction to a certain extent, graphene film interlayer existing defects, thus affect its performance in conductive and heat-conductive etc.Comparatively speaking, the laminated structure of grapheme material prepared by intercalation stripping method is more complete, lattice and surface imperfection less, therefore electrical and thermal conductivity performance is more excellent.Further, intercalation stripping method is in preparation process, and strong acid and the oxidizing species of use are fewer, can reduce the impact on environment.
But, under current technical qualification, no matter be adopt oxidation reduction process or intercalation stripping method to prepare Graphene, all adopt the vitriol oil as reaction medium in preparation process, the graphite expansion intermediate sulphur content that reaction produces reaches 3.1% ~ 4.5% [Zhang Ruijun, Liu Yingjie, Shen Wanci [J] carbon element .1997, (2): 24 ~ 28], therefore corresponding dissociate after the sulphur content of Graphene also can be too high, thus affect the range of application of Graphene prepared by these two kinds of methods.Graphene as employing redox or intercalation peeled off preparation is used for paint when metallic surface, has the effect promoting metallic corrosion; For also having a negative impact in environmental protection or medical material.Therefore, the breakthrough point that a kind of preparation method without sulfur graphite alkene becomes Graphene technical development is worked out.
Summary of the invention
The embodiment of the present invention provides a kind of preparation method of Graphene slurry, and object is to overcome graphene product sulphur content prepared by existing oxidation reduction process and intercalation stripping method and crosses the problems such as high.
Another object of the embodiment of the present invention is the application providing this Graphene slurry.
To achieve the above object of the invention, the technical scheme of embodiment of the present invention employing is as follows:
A preparation method for Graphene slurry, comprises the steps:
A, according to graphite: intercalator: oxygenant is 1g:(3 ~ 30) mL:(0.1 ~ 3.0) ratio of g takes reaction mass, then the described reaction mass taken is carried out batch mixing reaction treatment, through washing, drying treatment, obtain compound between graphite layers;
B, described compound between graphite layers is carried out puffing, obtain graphite expansion body;
C, be graphite expansion body by described graphite expansion body according to mass percent: dispersing auxiliary: solvent is (1.0 ~ 10.0): (0.1 ~ 2.0): 100.0 carry out mixing treatment and process of dissociating, acquisition Graphene slurry;
Wherein, described intercalator to be mass concentration be 65% ~ 98% nitric acid, mass concentration be 65% ~ 98% nitric acid and organic acid mixture, mass concentration be 65% ~ 98% nitric acid and mass concentration be any one in the phosphate mixture of 80% ~ 98%.
And correspondingly, a kind of lithium ion battery, the conductive agent material of this lithium ion battery is for being provided by the Graphene slurry adopting the preparation method of above-mentioned Graphene slurry to prepare.
And correspondingly, a kind of Graphene protective system, the filler component of this Graphene protective system is provided by the Graphene slurry adopting the preparation method of above-mentioned Graphene slurry to prepare.
In above-described embodiment, adopt natural flake graphite through peroxidation intercalation, expanded and process of dissociating, achieve the preparation of Graphene slurry.This preparation method's reaction conditions is gentle, and material reaction is abundant, easy and simple to handle, obtained Graphene slurry not sulfur-bearing, and the number of plies is few, can realize suitability for industrialized production.
The Graphene slurry of the preparation of above-described embodiment, in the conductive agent of lithium ion battery electrode material, effectively can reduce the addition of conductive agent.The more important thing is, by means of the conductivity that it is good, rate charge-discharge performance and the cycle performance of lithium ion battery can be increased substantially.
The Graphene slurry of the preparation of above-described embodiment, for in Graphene protective system, because of Graphene slurry not sulfur-bearing, existing Graphene coating promotes the metallic corrosion of painting face phenomenon because of sulfur-bearing can be overcome, improve the antiseptic property of Graphene coating greatly and expand the range of application of Graphene coating.
Accompanying drawing explanation
Fig. 1 is the Graphene slurry that the invention provides embodiment 1 preparation, and the graphene powder SEM obtained after washing, drying schemes.
Embodiment
Clearly understand that in order to make object of the present invention, technical scheme and advantage following examples are further elaborated to the present invention.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of preparation method of Graphene slurry, the preparation method of this Graphene slurry comprises the steps:
A, according to graphite: intercalator: oxygenant is 1g:(3 ~ 30) mL:(0.1 ~ 3.0) ratio of g takes reaction mass, then the described reaction mass taken is carried out batch mixing reaction treatment, again through washing, drying treatment, obtain compound between graphite layers;
B, described compound between graphite layers is carried out puffing, obtain graphite expansion body;
C, be graphite expansion body by described graphite expansion body according to mass percent: dispersing auxiliary: solvent is (1.0 ~ 10.0): (0.1 ~ 2.0): 100.0 carry out mixing treatment and process of dissociating, acquisition Graphene slurry.
Wherein, in one embodiment, the graphite in steps A adopts natural flake graphite.Natural flake graphite is hexagonal system, in laminate structure, is convenient to carry out oxidation intercalation processing.In one embodiment, natural flake graphite need through process of sieving, and choose order number when sieving at 30 ~ 2500 object screen clothes, the natural flake graphite within the scope of this order number, particle is moderate, can guarantee oxidation and intercalation thorough.In a specific embodiment, carbon content >=90% of natural flake graphite, can reduce other impurity existed in reaction process like this and cause impact on aspects such as reaction product purity.
In any embodiment, when batch mixing reaction treatment being carried out to reaction mass in steps A, first graphite should be mixed with intercalator, and then progressively repeatedly add oxygenant in batches.Such order of addition(of ingredients), is conducive to graphite and carries out fully mixing with intercalator and reach pre-reaction state; Progressively repeatedly add oxygenant in batches, the temperature of process and the reaction of reacting can be controlled, avoid crossing because of the disposable add-on of oxygenant mostly occurring vigorous oxidation and producing the side reaction that amount of heat may cause, the more important thing is, amount of heat effectively can be avoided not dispel the heat in time and cause runaway reaction and then may cause danger.
In one embodiment, described intercalator to be mass concentration be 65% ~ 98% nitric acid, mass concentration be 65% ~ 98% nitric acid and organic acid mixture, mass concentration be 65% ~ 98% nitric acid and mass concentration be any one in the phosphate mixture of 80% ~ 98%.Adopt the mixture of nitric acid or nitric acid and organic acid mixture or nitric acid and phosphoric acid as intercalator, instead of the vitriol oil, the Graphene not sulfur-bearing of preparation, can avoid because the existence of sulphur is on the impact of grapheme material performance.
In one embodiment, when intercalator be mass concentration is nitric acid and the organic acid mixture of 65% ~ 98%, described organic acid is any one in formic acid, acetic acid, propionic acid and butyric acid.
In one embodiment, oxygenant is strong oxidizer, can be specifically any one in potassium permanganate, ammonium persulphate, potassium bichromate, SODIUMNITRATE and hydrogen peroxide.
In one embodiment, the reactor that above-mentioned natural flake graphite, intercalator and oxygenant should be placed in dried and clean carries out oxidizing reaction, to ensure that in reaction process, reaction conditions is as the control of the reaction conditionss such as heating, stirring.
In one embodiment, the temperature of whole reaction should be controlled at 10 DEG C ~ 60 DEG C.When temperature of reaction is lower than 10 DEG C, the reactive behavior of reactant is low, and speed of reaction is slow, and preparation time lengthens, and is unfavorable for the efficient in order of production; When temperature of reaction is higher than 60 DEG C, because of the existence of concentrated nitric acid and other strong oxidizers, side reaction may occur, produce the toxic and harmfuls such as nitrogen protoxide, it is unfavorable to produce environmental protection, and it is out of control easily to react, wayward reaction process.
In one embodiment, protect in reaction process to hold and stir to promote heat radiation, avoid heat too much can not dispel the heat in time and side reaction occurs, the time controling of reaction and stirring is at 20 ~ 120min.
In one embodiment, in order to effectively control the mitigation degree of reaction process and control reaction, the access control of oxygenant at 20 ~ 100min, and the moment can keep whipped state when adding oxygenant.
In one embodiment, in order to reactive system temperature can be made to be reduced to room temperature and diluting reaction product fast to wash, at the end of reaction, be intercalator according to volume ratio: the ratio of deionized water=1:0.5 ~ 1:4, slowly adds deionized water.
In one specifically embodiment, question response system is down to room temperature, adopts centrifugal mode to carry out repetitive scrubbing, at least washs 4 times, then carries out drying treatment.
In one embodiment, during drying treatment, dry temperature controls at 40 DEG C ~ 100 DEG C.Drying temperature is too low, and time of drying is long, and drying efficiency is low; And when drying temperature is higher than 100 DEG C, reaction product fold or reunion easily occurs and restores the state before intercalation, intercalation effect is poor.More preferably in an embodiment, Freeze Drying Equipment can be adopted to carry out lyophilize.There is not fold or reunion in lyophilize product, can keep the Micro-surface condition after intercalation.
In any embodiment, the puffing of compound between graphite layers in step B, the time of puffing is 5s ~ 100s.Specifically can be undertaken by microwave or heat treatment mode.In one embodiment, when using microwave to carry out puffing, microwave power is 140W ~ 700W; When using thermal treatment to carry out expanded, heat treated temperature is 300 DEG C ~ 1000 DEG C.
In any embodiment, the dispersing auxiliary in step C is any one in Polyvinylpyrolidone (PVP), Sodium dodecylbenzene sulfonate, Sodium cholic acid, sodium lauryl sulphate, tween, Triton, polyvinyl alcohol.
In any embodiment, the solvent in step C is any one that N-methyl gives a tongue-lashing in pyrrolidone, DMF, N,N-dimethylacetamide, ethanol and deionized water.
In any embodiment, the process of dissociating of step C can be realized by any one in ball milling, sand mill colloidal mill.In one embodiment, the time of process of dissociating is 0.5h ~ 12h, to ensure to dissociate fully.
Graphene slurry prepared by aforesaid method embodiment of the present invention, only need through peroxidation intercalation, expanded and process of dissociating, the preparation of Graphene slurry can be realized, in whole preparation process without the need to the vitriol oil as reaction medium, reaction conditions is gentle, and material reaction is abundant, easy and simple to handle, the Graphene slurry not sulfur-bearing and the number of plies is few, very convenient suitability for industrialized production of preparation.
Correspondingly, the Graphene slurry that the embodiment of the present invention provides, can be used in the conductive agent of lithium ion battery electrode material.When the Graphene slurry that the conductive agent of lithium ion battery material is provided by the embodiment of the present invention provides, effectively can reduce the addition of conductive agent.Further, by means of it without sulphur feature, there is better conductivity, rate charge-discharge performance and the cycle performance of lithium ion battery can be increased substantially.
Correspondingly, the Graphene slurry that the embodiment of the present invention provides, can also as Graphene protective system.The Graphene slurry that filler component in described Graphene protective system is provided by the embodiment of the present invention provides.Described Graphene anti-corrosion paint, in metallic surface, can overcome existing Graphene protective system promotes the metallic corrosion of painting face phenomenon because of sulfur-bearing, and the range of application expanding Graphene protective system greatly also can improve the performance of Graphene protective system.
The preparation method of the above-mentioned Graphene slurry provided of the present invention is provided below by way of multiple embodiment.
Embodiment 1
The preparation of A, compound between graphite layers: according to natural flake graphite: nitric acid: KMnO
4=1g:20mL:0.8g, takes a certain amount of natural flake graphite, nitric acid and potassium permanganate respectively, and wherein, the natural flake graphite carbon content taken is 99.9%, 30 orders.The natural flake graphite taken is put in the reactor of dried and clean, then add the nitric acid that taken mass concentration is 98% wherein, and be uniformly mixed.Progressively in still, add taken KMnO in batches
4, and control temperature of reaction at 25 DEG C, stirring reaction 60min.Slowly add deionized water in the most backward reaction system, wherein, the deionized water volume added is 2 times of intercalator (nitric acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then in 60 DEG C of oven dry, obtains compound between graphite layers.
The preparation of B, graphite expansion body: dried compound between graphite layers is placed in retort furnace 900 DEG C of thermal treatment 30s.
The preparation of C, Graphene slurry: be graphite expansion body: PVP:NMP according to mass ratio be that 5.0:0.8:100 takes graphite expansion body, PVP and NMP.In stirred pot, add taken N-methyl give a tongue-lashing pyrrolidone (NMP), then the above-mentioned expanded good graphite expansion body taken in proportion and Polyvinylpyrolidone (PVP) (PVP) are added wherein, and by being uniformly mixed, finally by milling treatment of colloid 8h, obtain Graphene slurry.
Embodiment 2
The preparation of A, compound between graphite layers: according to natural flake graphite: the mixture of nitric acid and acetic acid: K
2cr
2o
7=1g:3mL:0.1g, take mixture and the potassium bichromate of a certain amount of natural flake graphite, nitric acid and acetic acid respectively, wherein, the natural flake graphite carbon content taken is 90%, 1000 orders, in the nitric acid taken and the mixture of acetic acid, the mass concentration of nitric acid is 65%, and the mass ratio of nitric acid and acetic acid is 1:1.The natural flake graphite taken is put in the reactor of dried and clean, then adds the mixture of taken nitric acid and acetic acid wherein, and be uniformly mixed.Progressively in still, add taken potassium bichromate in batches, and control temperature of reaction at 60 DEG C, stirring reaction 100min.Deionized water is slowly added in the most backward reaction system, wherein, the deionized water volume added is 2 times of intercalator (mixture of nitric acid and acetic acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then in 100 DEG C of oven dry, compound between graphite layers is obtained.
The preparation of B, graphite expansion body: undertaken expanded by microwave by dried compound between graphite layers, wherein microwave power is 700W, expanded time 60s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: Sodium dodecylbenzene sulfonate: DMF is that 10.0:2.0:100 takes graphite expansion body, Sodium dodecylbenzene sulfonate and DMF.Taken Sodium dodecylbenzene sulfonate is added in stirred pot, then the above-mentioned expanded good graphite expansion body taken in proportion and DMF are added wherein, and by being uniformly mixed, finally by ball-milling processing 12h, obtain Graphene slurry.
Embodiment 3
The preparation of A, compound between graphite layers: according to natural flake graphite: the mixture of nitric acid and phosphoric acid: (NH
4)
2s
2o
8=1g:10mL:2.5g, takes mixture and the over cure ammonium of a certain amount of natural flake graphite, nitric acid and phosphoric acid respectively, and wherein, the natural flake graphite carbon content taken is 95%, 2500 orders.In the nitric acid taken and the mixture of phosphoric acid, the mass concentration of nitric acid is 98%, and the mass concentration of phosphoric acid is 80%, and the mass ratio of nitric acid and phosphoric acid is 1:1.The natural flake graphite taken is put in the reactor of dried and clean, then add taken nitric acid and the mixture of phosphoric acid wherein, and be uniformly mixed.Progressively in still, add taken over cure ammonium in batches, and control temperature of reaction at 10 DEG C, stirring reaction 120min.Slowly add deionized water in the most backward reaction system, wherein, the deionized water volume added is identical with intercalator (nitric acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times, then dries under 40 DEG C of environment repeatedly, obtains compound between graphite layers.
The preparation of B, graphite expansion body: dried compound between graphite layers is placed in retort furnace 1000 DEG C of thermal treatment 5s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: Sodium cholic acid: N,N-dimethylacetamide is that 1.0:0.1:100 takes graphite expansion body, Sodium cholic acid and N,N-dimethylacetamide.In stirred pot, add taken Sodium cholic acid, then the above-mentioned expanded good graphite expansion body taken in proportion and N,N-dimethylacetamide are added wherein, and by being uniformly mixed, finally by milling treatment of colloid 0.5h, obtain Graphene slurry.
Embodiment 4
The preparation of A, compound between graphite layers: according to natural flake graphite: nitric acid: NaNO
3=1g:15mL:2.0g, takes a certain amount of natural flake graphite, nitric acid and peroxy-nitric acid sodium respectively, and wherein, the natural flake graphite carbon content taken is 92%, 50 orders.The nitric acid mass concentration taken is 65%.The natural flake graphite taken is put in the reactor of dried and clean, then adds taken nitric acid wherein, and be uniformly mixed.Progressively in still, add taken SODIUMNITRATE in batches, and control temperature of reaction at 50 DEG C, stirring reaction 20min.Deionized water is slowly added in the most backward reaction system, wherein, the deionized water volume added is 0.5 times of intercalator (nitric acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then in Freeze Drying Equipment, carry out lyophilize to completely dry, obtain compound between graphite layers.
The preparation of B, graphite expansion body: undertaken expanded by microwave by dried compound between graphite layers, wherein microwave power is 140W, expanded time 100s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: polyvinyl alcohol: ethanol is that 3.0:1.2:100 takes graphite expansion body, polyvinyl alcohol and ethanol.In stirred pot, add taken polyvinyl alcohol, then the above-mentioned expanded good graphite expansion body taken in proportion and ethanol are added wherein, and by being uniformly mixed, finally by ball-milling processing 10h, obtain Graphene slurry.
Embodiment 5
The preparation of A, compound between graphite layers: according to natural flake graphite: the mixture of nitric acid and propionic acid: H
2o
2ratio be 1g:12mL:2.5g, take mixture and the potassium bichromate of a certain amount of natural flake graphite, nitric acid and acetic acid respectively, wherein, the natural flake graphite carbon content taken is 98%, 80 orders, in the nitric acid taken and the mixture of acetic acid, the mass concentration of nitric acid is 98%, and the mass ratio of nitric acid and propionic acid is 1:1.The natural flake graphite taken is put in the reactor of dried and clean, then adds the mixture of taken nitric acid and acetic acid wherein, and be uniformly mixed.Progressively in still, add taken hydrogen peroxide in batches, and control temperature of reaction at 30 DEG C, stirring reaction 40min.Deionized water is slowly added in the most backward reaction system, wherein, the deionized water volume added is 4 times of intercalator (mixture of nitric acid and acetic acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then dry under 80 DEG C of environment, obtain compound between graphite layers.
The preparation of B, graphite expansion body: dried compound between graphite layers is placed in retort furnace, 300 DEG C of thermal treatment 80s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: tween: the ratio that N-methyl gives a tongue-lashing pyrrolidone is that 8.0:1.0:100 takes graphite expansion body, tween, and N-methyl gives a tongue-lashing pyrrolidone.In stirred pot, add taken tween, then the above-mentioned expanded good graphite expansion body taken in proportion and N-methyl are given a tongue-lashing pyrrolidone and add wherein, and by being uniformly mixed, finally by milling treatment of colloid 2h, obtain Graphene slurry.
Embodiment 6
The preparation of A, compound between graphite layers: according to natural flake graphite: nitric acid and formic acid: (NH
4)
2s
2o
8=1g:12mL:0.8g, takes mixture and the over cure ammonium of a certain amount of natural flake graphite, nitric acid and formic acid respectively, and wherein, the natural flake graphite carbon content taken is 98%, 300 orders.In the nitric acid taken and the mixture of formic acid, the mass concentration of nitric acid is 85%, and the mass ratio of nitric acid and formic acid is 1:1.The natural flake graphite taken is put in the reactor of dried and clean, then add taken nitric acid and the mixture of formic acid wherein, and be uniformly mixed.Progressively in still, add taken over cure ammonium in batches, and control temperature of reaction at 35 DEG C, stirring reaction 45min.Deionized water is slowly added in the most backward reaction system, wherein, the deionized water volume added is 3 times of intercalator (nitric acid and formic acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then carry out lyophilize in Freeze Drying Equipment, obtain compound between graphite layers.
The preparation of B, graphite expansion body: dried compound between graphite layers is placed in retort furnace 500 DEG C of thermal treatment 40s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: Triton: it is that 6.0:1.2:100 takes graphite expansion body, Triton and N-methyl and gives a tongue-lashing pyrrolidone that N-methyl gives a tongue-lashing pyrrolidone.In stirred pot, add taken Triton, then the above-mentioned expanded good graphite expansion body taken in proportion and N-methyl are given a tongue-lashing pyrrolidone and add wherein, and by being uniformly mixed, finally by milling treatment of colloid 6h, obtain Graphene slurry.
Embodiment 7
The preparation of A, compound between graphite layers: according to natural flake graphite: the mixture of nitric acid and butyric acid: KMnO
4=1g:28mL:2.6g, takes mixture and the potassium permanganate of a certain amount of natural flake graphite, nitric acid and butyric acid respectively, and wherein, the natural flake graphite carbon content taken is 97%, 800 orders.In the nitric acid taken and the mixture of butyric acid, the mass concentration of nitric acid is 92%, and the mass ratio of nitric acid and butyric acid is 1:1.The natural flake graphite taken is put in the reactor of dried and clean, then add taken nitric acid and the mixture of butyric acid wherein, and be uniformly mixed.Progressively in still, add taken potassium permanganate in batches, and control temperature of reaction at 20 DEG C, stirring reaction 35min.Deionized water is slowly added in the most backward reaction system, wherein, the deionized water volume added is 2 times of intercalator (mixture of nitric acid and butyric acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then in 70 DEG C of oven dry, compound between graphite layers is obtained.
The preparation of B, graphite expansion body: dried compound between graphite layers is placed in retort furnace 700 DEG C of thermal treatment 25s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: Polyvinylpyrolidone (PVP): DMF is that 4.0:0.75:100 takes graphite expansion body, Polyvinylpyrolidone (PVP) and DMF.Taken Polyvinylpyrolidone (PVP) is added in stirred pot, then the above-mentioned expanded good graphite expansion body taken in proportion and DMF are added wherein, and by being uniformly mixed, finally by ball-milling processing 2h, obtain Graphene slurry.
Embodiment 8
The preparation of A, compound between graphite layers: according to natural flake graphite: the mixture of nitric acid and phosphoric acid: NaNO
3=1g:20mL:2.5g, takes mixture and the SODIUMNITRATE of a certain amount of natural flake graphite, nitric acid and phosphoric acid respectively, and wherein, the natural flake graphite carbon content taken is 96%, 1500 orders.In the nitric acid taken and the mixture of phosphoric acid, the mass concentration of nitric acid is 65%, and the mass concentration of phosphoric acid is 98%, and the mass ratio of nitric acid and phosphoric acid is 1:1.The natural flake graphite taken is put in the reactor of dried and clean, then add taken nitric acid and the mixture of phosphoric acid wherein, and be uniformly mixed.Progressively in still, add taken SODIUMNITRATE in batches, and control temperature of reaction at 45 DEG C, stirring reaction 50min.Deionized water is slowly added in the most backward reaction system, wherein, the deionized water volume added is 1.5 times of intercalator (mixture of nitric acid and phosphoric acid) volume, after the temperature of question response mixture is down to room temperature, centrifugal washing 4 times repeatedly, then in 60 DEG C of oven dry, compound between graphite layers is obtained.
The preparation of B, graphite expansion body: undertaken expanded by microwave by dried compound between graphite layers, wherein microwave power is 600W, expanded time 5s.
The preparation of C, Graphene slurry: be graphite expansion body according to mass ratio: sodium lauryl sulphate: H
2o is that 8.0:1.8:100 takes graphite expansion body, sodium lauryl sulphate and deionized water.In stirred pot, add taken sodium lauryl sulphate, then the above-mentioned expanded good graphite expansion body taken in proportion and deionized water are added wherein, and by being uniformly mixed, finally by sanded 3h, obtain Graphene slurry.
In order to verify that Graphene slurry that the embodiment of the present invention provides is for role in lithium ion battery material conductive agent, the Graphene slurry additionally providing embodiment 1 preparation makes the comparative example of battery as lithium ion battery conductive agent and conventional carbon black as lithium ion battery conductive agent, specific as follows:
Experimental group: be LiFePO 4 according to mass ratio: Graphene slurry: PVDF=95: 2: 3, takes LiFePO 4, Graphene slurry and PVDF, make solvent with NMP, wherein, the Graphene slurry that Graphene slurry provides for the embodiment of the present invention 1.Then in stirrer, stir 2h with 2000rpm rotating speed, the slurry after mixing is applied on aluminium foil, dry at 120 DEG C, then through roll-in, obtain anode slice of lithium ion battery; Again through cut-parts, with barrier film and cathode pole piece reels in order, fluid injection, packaging process, obtained 18650 cylindrical batteries, carry out electrochemical property test.
Control experiment group: be ferrous phosphate doping lithium anode material, carbon black, PVDF=95: 2: 3 according to mass ratio, take ferrous phosphate doping lithium anode material, carbon black and PVDF, make solvent with NMP, wherein, carbon black is conventional conductive carbon black.Then in stirrer, stir 2h with 2000rpm rotating speed, the slurry after mixing is applied on aluminium foil, dry at 120 DEG C, then through roll-in, obtain anode slice of lithium ion battery; Again through cut-parts, with barrier film and cathode pole piece reels in order, fluid injection, packaging process, 18650 cylindrical batteries of obtained comparative example, carry out electrochemical property test.
The negative material that above-mentioned experimental group and control group adopt is carbonaceous mesophase spherules MCMB, and barrier film is Celgard2400, and electrolytic solution is 1MLiPF
6/ EC+PC+EMC.The electric performance test of experimental group and control group is in table 1.
Table 1 embodiment 1 and comparative example electric performance test result.
| Test event | The internal resistance of cell (m Ω) | 2C/1C | 5C/1C | 10C/1C | Capability retention after circulating under 2.0 ~ 3.6V/1C condition 500 weeks |
| Experimental group | 18 | 93.5％ | 86.6％ | 75.3％ | 97％ |
| Control group | 40 | 89.4％ | 83.7％ | 72.8％ | 92％ |
As can be seen from the table, the Graphene slurry adopting the embodiment of the present invention to provide has lower internal resistance, better high rate performance and cycle performance as the lithium ion battery of conductive agent.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for Graphene slurry, is characterized in that: comprise the following steps:
A, according to graphite: intercalator: oxygenant is 1g:(3 ~ 30) mL:(0.1 ~ 3.0) ratio of g takes reaction mass, then the described reaction mass taken is carried out batch mixing reaction treatment, through washing, drying treatment, obtain compound between graphite layers;
B, described compound between graphite layers is carried out puffing, obtain graphite expansion body;
C, be graphite expansion body by described graphite expansion body according to mass percent: dispersing auxiliary: solvent is (1.0 ~ 10.0): (0.1 ~ 2.0): 100.0 carry out mixing treatment and process of dissociating, acquisition Graphene slurry;
Wherein, described intercalator to be mass concentration be 65% ~ 98% nitric acid, mass concentration be 65% ~ 98% nitric acid and organic acid mixture, mass concentration be 65% ~ 98% nitric acid and mass concentration be any one in the phosphate mixture of 80% ~ 98%.
2. the preparation method of Graphene slurry as claimed in claim 1, is characterized in that: described oxygenant is any one in potassium permanganate, ammonium persulphate, potassium bichromate, SODIUMNITRATE and hydrogen peroxide.
3. the preparation method of the Graphene slurry as described in as arbitrary in claim 1 ~ 2, is characterized in that: the temperature of described step A reaction treatment is 10 DEG C ~ 60 DEG C.
4. the preparation method of the Graphene slurry as described in as arbitrary in claim 1 ~ 2, is characterized in that: described graphite is order number 30 ~ 2500 order, the natural flake graphite of carbon content >=90%.
5. the preparation method of the Graphene slurry as described in as arbitrary in claim 1 ~ 2, is characterized in that: the described puffing time is 5s ~ 100s, and adopts microwave treatment or thermal treatment to carry out expanded; Wherein, the microwave power of described microwave treatment is 140W ~ 700W, and described heat treated temperature is 300 DEG C ~ 1000 DEG C.
6. the preparation method of the Graphene slurry as described in as arbitrary in claim 1 ~ 2, is characterized in that: described dispersing auxiliary is any one in Polyvinylpyrolidone (PVP), Sodium dodecylbenzene sulfonate, Sodium cholic acid, sodium lauryl sulphate, tween, Triton, polyvinyl alcohol.
7. the preparation method of the Graphene slurry as described in as arbitrary in claim 1 ~ 2, is characterized in that: described solvent is any one that N-methyl gives a tongue-lashing in pyrrolidone, DMF, N,N-dimethylacetamide, ethanol and deionized water.
8. a lithium ion battery, is characterized in that: the conductive agent material of described lithium ion battery is provided by the Graphene slurry prepared according to the arbitrary described graphite slurry preparation method of claim 1 ~ 7.
9. a Graphene protective system, is characterized in that: the filler component of described Graphene protective system is provided by the Graphene slurry prepared according to the arbitrary described graphite slurry preparation method of claim 1 ~ 7.
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