CN103178243A - Graphene/metal composite negative electrode material for lithium ion battery and preparation method of graphene/metal composite negative electrode material - Google Patents
Graphene/metal composite negative electrode material for lithium ion battery and preparation method of graphene/metal composite negative electrode material Download PDFInfo
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Abstract
The invention relates to a graphene/metal composite negative electrode material for a lithium ion battery and a preparation method of the graphene/metal composite negative electrode material. The preparation method comprises the following steps of: preparing a metal electrode with an optical grating structure by chemical etching, preparing graphene/titanium dioxide composite particles by using a redoxchemistry method, depositing the graphene/titanium dioxide composite particles on the metal electrode with the optical grating structure, and carrying out further heat treatment to obtain the graphene/metal composite negative electrode material. According to the graphene/metal composite negative electrode material and the preparation method, the nano titanium dioxide particles are used for modifying the stacking of graphene, and the metal optical grating structure is used as a graphene carrier, so that the graphene can be vertical to a current collector to be arranged into an array; by virtue of the structure, the diffusion distance of lithium ions among graphene sheets is shortened, and meanwhile, the lithium ions can be embedded and withdrawn among the graphene sheets more rapidly; and therefore, the graphene/metal composite negative electrode material has high specific capacity, excellent cycling stability and rate capability when being used as a negative electrode of a lithium ion battery and is hopeful to be used as a negative electrode material, with high energy density and high power density, of the lithium ion battery.
Description
Technical field
The invention belongs to the synthetic energy technology field that reaches of material, particularly relate to a kind of lithium ion battery Graphene/metal composite negative pole material and preparation method thereof.
Background technology
By the standby New Type of Carbon material of graphite-made, individual layer or thin layer graphite (multi-layer graphenes of 2～10 layers) application potential in chemical power source also receives much concern Graphene as a kind of.Graphene is the monolayer carbon atom, and upper and lower surface all can be stored lithium ion, and itself can be used as lithium ion battery negative material; Simultaneously due to very good mechanical properties and the electric conductivity of Graphene, also be commonly used to other negative materials compound, to improve electrode performance.
Graphene has excellent chemical property, and many researchers wish by Graphene and the compound purpose that reaches in field practical applications such as electrochemistry of other materials.Be dissolved in ethylene glycol Graphene compound with the nano-stannic oxide of rutile structure as Paek etc., form composite porous, it is carried out electro-chemical test as electrode, result shows that the reversible capacity of this composite material is 810mAh/g, compare with pure nano-stannic oxide particle, cycle performance be improved significantly, 30 times the circulation after, charging capacity is 570mAh/g, and the reversible capacity conservation rate is 70%; And pure nano-stannic oxide particle initial charge specific capacity is 550mAh/g, decays to rapidly 60mAh/g after 15 circulations.This is mainly because nano-stannic oxide particle inserts in Graphene space between layers fully, in cyclic process, when lithium inserts in the tin ash lattice, the stable skeleton of Graphene has cushioned the volumetric expansion of tin ash lattice, and Graphene has become cushion space just with space between stannic oxide particle, and this makes material have good cycle performance.Wang etc. have synthesized titanium dioxide-Graphene hybrid material, and the insertion performance of having tested lithium ion, result shows, hybrid material has obviously strengthened lithium ion and taken off slotting ability in titanium dioxide, under high charge rate, its specific capacity is 2 times of pure titinium dioxide, and this is mainly obviously to have improved the conductivity of material due to the existence of Graphene.
But, because the Graphene search time is short, belong to the new material system, still have some problems in lithium ion battery field application at present: in (1) Graphene preparation process, lamella is easily piled up, and has reduced theoretical capacity; (2) a kind of comparatively ideal structure is that graphene sheet layer is all lined up array perpendicular to collector, this structure had both reduced the diffusion length of lithium ion between graphene sheet layer, also make simultaneously lithium ion in the embedding of graphene film interlayer, deviate from faster, but the structure of this structure is more difficult.
In sum, the structure of matter of Graphene uniqueness and excellent chemical property, it is had a good application prospect in the lithium ion battery field, but at present still there is the technical difficulty of the aspects such as preparation and application in Graphene, makes its practical application in the lithium ion battery field also have larger distance.
Summary of the invention
The present invention is directed to the Graphene negative material that existing lithium ion battery uses and easily superpose, and be difficult to and the problems such as collector is vertical, the Graphene negative material that the lithium ion battery of design and a kind of new construction of preparation material is used, concrete structure as shown in Figure 1:
The Graphene negative material of new structure of the present invention is to adopt following technical scheme to realize:
A kind of lithium ion battery is characterized by with Graphene/metal composite negative pole material, and described composite negative pole material is comprised of metal and Graphene/titanium dioxide, and wherein Graphene/titanium dioxide is compound perpendicular to sheet metal, and its structure as shown in Figure 1 and Figure 2.
The present invention provides the preparation method of a kind of lithium ion battery with Graphene/metal composite negative pole material simultaneously, and step is as follows:
(1) under condition of ice bath, 0.5～5.0g graphite is joined in the concentrated sulfuric acid of 40ml～60ml strong agitation 30min; Further with 12～30g KMnO
4Join in above-mentioned mixed liquor strong agitation 30min; Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18～40gNaNO
3, stir 60min; Under stirring state, 100～140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 12～20mlH
2O
2, continue reaction 40min～80min until solution becomes glassy yellow from dark-brown; Under stirring condition, add a certain amount of polymethyl acrylate PAA to disperse reagent in above-mentioned glassy yellow graphene oxide solution, drip the hydrazine hydrate solution of 15～45ml after dissolving, react 1h at 40 ℃～80 ℃ temperature; Further drip also original reagent of 15～45ml in mentioned solution, continue reaction 20～60min, obtain stable graphene aqueous solution;
(2) regulating above-mentioned graphene aqueous solution to pH value with nitric acid is 3～6, then a certain amount of titanium tetraisopropylate is mixed with isopropyl alcohol or ethanol, at room temperature mixed liquor is slowly splashed in above-mentioned graphene solution, and constantly stirs; Drip off and rise to rapidly 60 ℃～80 ℃ afterwards, reaction 10～30min, adding ammoniacal liquor regulator solution pH value is 11～13, can obtain the stable Graphene that high-performance electric deposits use/titanium dioxide compound aqueous solution;
(3) spraying 2 μ m thick polymer films on sheet metal or paper tinsel, impress under the template of certain size optical grating construction, spray again nitric acid or sulfuric acid that concentration is 20～50wt%, after etching 2～10h, put into and remove polymer film in organic solvent, can form in the metal surface optical grating construction of certain pattern and size;
(4) with the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then freshly prepd Graphene/titanium dioxide compound aqueous solution is poured in electrophoresis tank, turn on the power switch, under certain electrode spacing, deposition voltage, sedimentation time condition, electrophoretic deposition Graphene/titanium dioxide complex particle in the electrode optical grating construction; And place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully; Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
The preparation method of described composite negative pole material, in (1) step, it is 0.5～20wt% that PAA disperses the concentration of aqueous solution of reagent.
The preparation method of described composite negative pole material, in (1) step, the described original reagent of going back is acetic acid or hydroiodic acid; Acetic acid aqueous solution concentration is 10～30wt%, and hydriodic acid aqueous solution concentration is 10～40wt%.
The preparation method of described composite negative pole material, in (2) step, the consumption of titanium tetraisopropylate is 0.2～3.0g, the consumption of isopropyl alcohol or ethanol is 5～20ml.
The preparation method of described composite negative pole material, in its (3) step, metal is aluminium, copper, zinc, tin and lead etc.
The preparation method of described composite negative pole material, in (3) step,, metal grating structure is as the Graphene carrier, make it to line up array perpendicular to collector, wherein the live width of optical grating construction (as shown in Figure 3) be 5～50nm, spacing wide be 20～10 μ m, highly be 10～50 μ m.
The preparation method of described composite negative pole material, in (4) step, new configuration Graphene/titanium dioxide composite suspension liquid concentration is 0.5-10wt%.
The preparation method of described composite negative pole material, in (4) step, electrode spacing, sedimentation time, deposition voltage are respectively 10～25mm, 5min～30min, 10V～100V.
Advantage of the present invention is:
1, the electrode in the present invention, Graphene is vertical with collector, makes the diffusion of lithium ion between graphene sheet layer unobstructed, is conducive to the diffusion transport of lithium ion.Therefore, graphene-based electrode material has good electron propagation ducts and ion transfer passage simultaneously, is very beneficial for the raising of lithium ion battery power-performance.
2, the electrode in the present invention is that high Graphene/titanium dioxide is compound, adopt simple hydro thermal method to prepare, can effectively control titanium dioxide nano-particle load on graphene film, prevent the stack of graphene film, improve electric transmission speed and ionic adsorption efficient.
3, the Fabrication Technology of Electrode in the present invention adopts electro-deposition techniques, has simplified production process, has reduced production cost, has improved production efficiency, can continuity operate, and has industrial value.
Description of drawings
Fig. 1 Graphene/metal composite electrode structure schematic diagram
Fig. 2 is the enlarged diagram at A place in Fig. 1
The sheet metal schematic diagram of Fig. 3 optical grating construction
In figure, 1 is Graphene, and 2 is titanium dioxide, and 3 is metal, and 4 is Graphene/titanium dioxide (namely 1 and 2).
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Under condition of ice bath, 3.0g graphite is joined in the concentrated sulfuric acid of 60ml, strong agitation 30min is further with 12gKMnO
4Join in above-mentioned mixed liquor strong agitation 30min.Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18gNaNO
3, stir 60min; Under stirring state, the 140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 18mlH
2O
2, continue reaction 60min and make solution become glassy yellow from dark-brown;
Under stirring condition, adding consumption in above-mentioned graphene oxide solution is the dispersion reagent PAA of the 1.5wt% of graphene oxide, drip the hydrazine hydrate solution of 20ml after dissolving, react 1h at 60 ℃ of temperature, further drip the 20ml20wt% acetic acid aqueous solution in mentioned solution, continue reaction 30min, obtain stable graphene aqueous solution.
Regulating above-mentioned graphene aqueous solution pH with nitric acid is 3, and then titanium tetraisopropylate and the 10ml isopropyl alcohol with 0.4g mixes, and at room temperature mixed liquor slowly splashed in above-mentioned graphene solution, and constantly stirs.Drip off and rise to rapidly 70 ℃ afterwards, reaction 10min, adding ammoniacal liquor regulator solution pH value is 11, can obtain the stable graphene solution that high-performance electric deposits use.
The spraying 9 thick polymer films of μ m on sheet metal or metal forming, be 10nm in live width, spacing is wide is 2 μ m, be highly to impress under the template of 10 μ m optical grating constructions, then spray the sulfuric acid that concentration is 20wt%, after etching 2h, put into and remove polymer film in organic solvent, can form live width is 10nm, and spacing is wide is 2 μ m, is highly the optical grating construction sheet metal of 15 μ m.
With the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then the Graphene of new configuration/titanium dioxide composite suspension liquid 20ml is poured in electrophoresis tank, turn on the power switch, at 15mm, deposition voltage 10V, sedimentation time 5min.After electrophoretic deposition is completed, take out electrode, and place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully.Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
Under condition of ice bath, 3.0g graphite is joined in the concentrated sulfuric acid of 60ml, strong agitation 30min is further with 12gKMnO
4Join in above-mentioned mixed liquor strong agitation 30min.Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18gNaNO
3, stir 60min; Under stirring state, the 140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 18mlH
2O
2, continue reaction 60min and make solution become glassy yellow from dark-brown;
Under stirring condition, adding consumption in above-mentioned graphene oxide solution is the dispersion reagent PAA of the 2.5wt% of graphene oxide, drip the hydrazine hydrate solution of 20ml after dissolving, react 1h at 80 ℃ of temperature, further drip the 20ml10wt% acetic acid aqueous solution in mentioned solution, continue reaction 40min, obtain stable graphene aqueous solution.
Regulating above-mentioned graphene aqueous solution pH with nitric acid is 5, and then titanium tetraisopropylate and the 10ml isopropyl alcohol with 0.7g mixes, and at room temperature mixed liquor slowly splashed in above-mentioned graphene solution, and constantly stirs.Drip off and rise to rapidly 70 ℃ afterwards, reaction 10min, adding ammoniacal liquor regulator solution pH value is 12, can obtain the stable graphene solution that high-performance electric deposits use.
The spraying 9 thick polymer films of μ m on sheet metal or metal forming, be 10nm in live width, spacing is wide is 2 μ m, be highly to impress under the template of 10 μ m optical grating constructions, then spray the sulfuric acid that concentration is 30wt%, after etching 4h, put into and remove polymer film in organic solvent, can form live width is 10nm, and spacing is wide is 2 μ m, is highly the optical grating construction sheet metal of 20 μ m.
With the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then the Graphene of new configuration/titanium dioxide composite suspension liquid 20ml is poured in electrophoresis tank, turn on the power switch, at 15mm, deposition voltage 20V, sedimentation time 10min.After electrophoretic deposition is completed, take out electrode, and place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully.Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
Under condition of ice bath, 3.0g graphite is joined in the concentrated sulfuric acid of 60ml, strong agitation 30min is further with 12gKMnO
4Join in above-mentioned mixed liquor strong agitation 30min.Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18gNaNO
3, stir 60min; Under stirring state, the 140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 18mlH
2O
2, continue reaction 60min and make solution become glassy yellow from dark-brown;
Under stirring condition, adding consumption in above-mentioned graphene oxide solution is the dispersion reagent PAA of the 2.5wt% of graphene oxide, drip the hydrazine hydrate solution of 20ml after dissolving, react 1h at 80 ℃ of temperature, further drip the 20ml15wt% acetic acid aqueous solution in mentioned solution, continue reaction 50min, obtain stable graphene aqueous solution.
Regulating above-mentioned graphene aqueous solution pH with nitric acid is 5, and then titanium tetraisopropylate and the 10ml isopropyl alcohol with 1.7g mixes, and at room temperature mixed liquor slowly splashed in above-mentioned graphene solution, and constantly stirs.Drip off and rise to rapidly 70 ℃ afterwards, reaction 20min, adding ammoniacal liquor regulator solution pH value is 13, can obtain the stable graphene solution that high-performance electric deposits use.
The spraying 9 thick polymer films of μ m on sheet metal or metal forming, be 10nm in live width, spacing is wide is 2 μ m, be highly to impress under the template of 10 μ m optical grating constructions, then spray the sulfuric acid that concentration is 30wt%, after etching 5h, put into and remove polymer film in organic solvent, can form live width is 10nm, and spacing is wide is 2 μ m, is highly the optical grating construction sheet metal of 30 μ m.
With the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then the Graphene of new configuration/titanium dioxide composite suspension liquid 20ml is poured in electrophoresis tank, turn on the power switch, at 15mm, deposition voltage 40V, sedimentation time 20min.After electrophoretic deposition is completed, take out electrode, and place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully.Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
Under condition of ice bath, 3.0g graphite is joined in the concentrated sulfuric acid of 60ml, strong agitation 30min is further with 12gKMnO
4Join in above-mentioned mixed liquor strong agitation 30min.Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18gNaNO
3, stir 60min; Under stirring state, the 140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 18mlH
2O
2, continue reaction 60min and make solution become glassy yellow from dark-brown;
Under stirring condition, adding consumption in above-mentioned graphene oxide solution is the dispersion reagent PAA of the 4.5wt% of graphene oxide, drip the hydrazine hydrate solution of 20ml after dissolving, react 1h at 70 ℃ of temperature, further drip the 20ml10wt% acetic acid aqueous solution in mentioned solution, continue reaction 40min, obtain stable graphene aqueous solution.
Regulating above-mentioned graphene aqueous solution pH with nitric acid is 4, and then titanium tetraisopropylate and the 20ml isopropyl alcohol with 2.7g mixes, and at room temperature mixed liquor slowly splashed in above-mentioned graphene solution, and constantly stirs.Drip off and rise to rapidly 80 ℃ afterwards, reaction 30min, adding ammoniacal liquor regulator solution pH value is 13, can obtain the stable graphene solution that high-performance electric deposits use.
The spraying 9 thick polymer films of μ m on sheet metal or metal forming, be 10nm in live width, spacing is wide is 2 μ m, be highly to impress under the template of 10 μ m optical grating constructions, then spray the sulfuric acid that concentration is 30wt%, after etching 5h, put into and remove polymer film in organic solvent, can form live width is 10nm, and spacing is wide is 2 μ m, is highly the optical grating construction sheet metal of 35 μ m.
With the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then the Graphene of new configuration/titanium dioxide composite suspension liquid 20ml is poured in electrophoresis tank, turn on the power switch, at 20mm, deposition voltage 20V, sedimentation time 5min.After electrophoretic deposition is completed, take out electrode, and place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully.Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
Embodiment 5
Under condition of ice bath, 3.0g graphite is joined in the concentrated sulfuric acid of 60ml, strong agitation 30min is further with 12gKMnO
4Join in above-mentioned mixed liquor strong agitation 30min.Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18gNaNO
3, stir 60min; Under stirring state, the 140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 18mlH
2O
2, continue reaction 60min and make solution become glassy yellow from dark-brown;
Under stirring condition, adding consumption in above-mentioned graphene oxide solution is the dispersion reagent PVP of the 4.5wt% of graphene oxide, drip the hydrazine hydrate solution of 20ml after dissolving, react 1h at 40 ℃ of temperature, further drip the 20ml40wt% hydriodic acid aqueous solution in mentioned solution, continue reaction 40min, obtain stable graphene aqueous solution.
Regulating above-mentioned graphene aqueous solution pH with nitric acid is 3, and then titanium tetraisopropylate and the 30ml ethanol with 0.7g mixes, and at room temperature mixed liquor is slowly splashed in above-mentioned graphene solution, and constantly stirs.Drip off and rise to rapidly 80 ℃ afterwards, reaction 20min, adding ammoniacal liquor regulator solution pH value is 13, can obtain the stable graphene solution that high-performance electric deposits use.
The spraying 9 thick polymer films of μ m on sheet metal or metal forming, be 10nm in live width, spacing is wide is 2 μ m, be highly to impress under the template of 10 μ m optical grating constructions, then spray the sulfuric acid that concentration is 30wt%, after etching 10h, put into and remove polymer film in organic solvent, can form live width is 10nm, and spacing is wide is 2 μ m, is highly the optical grating construction sheet metal of 55 μ m.
With the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then the Graphene of new configuration/titanium dioxide composite suspension liquid 20ml is poured in electrophoresis tank, turn on the power switch, at 20mm, deposition voltage 80V, sedimentation time 20min.After electrophoretic deposition is completed, take out electrode, and place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully.Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
Table 1. coating preparation gets conduction and the mechanical property of coating
Claims (10)
1. a lithium ion battery with Graphene/metal composite negative pole material, is characterized by, and described composite negative pole material is comprised of metal and Graphene/titanium dioxide, and wherein Graphene/titanium dioxide is compound perpendicular to sheet metal.
2. the preparation method of a lithium ion battery use Graphene/metal composite negative pole material, is characterized in that, step is as follows:
(1) under condition of ice bath, 0.5～5.0g graphite is joined in the concentrated sulfuric acid of 40ml～60ml strong agitation 30min; Further with 12～30g KMnO
4Join in above-mentioned mixed liquor strong agitation 30min; Above-mentioned mixed liquor is transferred in 30 ℃ of water-baths, slowly added 18～40gNaNO
3, stir 60min; Under stirring state, 100～140ml deionized water is joined in above-mentioned mixed liquor continuously, then it is transferred in the oil bath with 90 ℃ of temperature, stir the 30min time; Dropwise add again 12～20mlH
2O
2, continue reaction 40min～80min until solution becomes glassy yellow from dark-brown; Under stirring condition, add a certain amount of polymethyl acrylate PAA to disperse reagent in above-mentioned glassy yellow graphene oxide solution, drip the hydrazine hydrate solution of 15～45ml after dissolving, react 1h at 40 ℃～80 ℃ temperature; Further drip also original reagent of 15～45ml in mentioned solution, continue reaction 20～60min, obtain stable graphene aqueous solution;
(2) regulating above-mentioned graphene aqueous solution to pH value with nitric acid is 3～6, then a certain amount of titanium tetraisopropylate is mixed with isopropyl alcohol or ethanol, at room temperature mixed liquor is slowly splashed in above-mentioned graphene solution, and constantly stirs; Drip off and rise to rapidly 60 ℃～80 ℃ afterwards, reaction 10～30min, adding ammoniacal liquor regulator solution pH value is 11～13, can obtain the stable Graphene that high-performance electric deposits use/titanium dioxide compound aqueous solution;
(3) spraying 2 μ m thick polymer films on sheet metal or paper tinsel, impress under the template of certain size optical grating construction, spray again nitric acid or sulfuric acid that concentration is 20～50wt%, after etching 2～10h, put into and remove polymer film in organic solvent, can form in the metal surface optical grating construction of certain pattern and size;
(4) with the sheet metal of above-mentioned optical grating construction or the paper tinsel electrode as electrophoretic deposition, the one side of conduction is staggered relatively, then freshly prepd Graphene/titanium dioxide compound aqueous solution is poured in electrophoresis tank, turn on the power switch, under certain electrode spacing, deposition voltage, sedimentation time condition, electrophoretic deposition Graphene/titanium dioxide complex particle in the electrode optical grating construction; And place it in 120 ℃ of baking ovens to bone dry, the water that is present in electrode surface is volatilized fully; Then, the heating rate with 250 ℃/h carries out annealing in process at a certain temperature in annealing furnace.
3. the preparation method of composite negative pole material as claimed in claim 2, is characterized in that, in (1) step, it is 0.5～20wt% that PAA disperses the concentration of aqueous solution of reagent.
4. the preparation method of composite negative pole material as claimed in claim 2, is characterized in that, in (1) step, the described original reagent of going back is acetic acid or hydroiodic acid; Acetic acid aqueous solution concentration is 10～30wt%, and hydriodic acid aqueous solution concentration is 10～40wt%.
5. the preparation method of composite negative pole material as claimed in claim 2, is characterized in that, in (2) step, the consumption of titanium tetraisopropylate is 0.2～3.0g, and the consumption of isopropyl alcohol or ethanol is 5～20ml.
6. the preparation method of composite negative pole material as claimed in claim 2, is characterized in that, in (3) step, metal is aluminium, copper, zinc, tin and lead.
7. the preparation method of composite negative pole material as claimed in claim 2, it is characterized in that, in (3) step, metal grating structure is as the Graphene carrier, make it to line up array perpendicular to collector, wherein the live width of optical grating construction be 5～50nm, spacing wide be 20～10 μ m, highly be 10～50 μ m.
8. the preparation method of composite negative pole material as claimed in claim 2, is characterized in that, in (4) step, new configuration Graphene/titanium dioxide composite suspension liquid concentration is 0.5-10wt%.
9. the preparation method of composite negative pole material as claimed in claim 2, is characterized in that, in (4) step, electrode spacing, sedimentation time, deposition voltage are respectively 10～25mm, 5min～30min, 10V～100V.
10. a lithium ion battery with Graphene/metal composite negative pole material, is characterized in that, described lithium ion battery is prepared by the described preparation method of any one in claim 2 to 9 with Graphene/metal composite negative pole material.
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| CN110550597A (en) * | 2019-02-12 | 2019-12-10 | 深圳市溢鑫科技研发有限公司 | vertical few-layer graphene-metal nanoparticle composite catalytic electrode |
| CN110085428A (en) * | 2019-05-14 | 2019-08-02 | 南京邮电大学 | A kind of compound light anode of titanium dioxide/graphene and preparation method thereof |
| CN112467123A (en) * | 2020-08-14 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | High-capacity lithium ion battery cathode material and preparation method thereof |
| CN113178569A (en) * | 2021-03-22 | 2021-07-27 | 黑龙江工业学院 | Preparation method of pillared layer carrier semiconductor type natural graphite composite lithium battery negative electrode material |
| CN114214690A (en) * | 2021-12-27 | 2022-03-22 | 宁波南大光电材料有限公司 | Electroplating method for plating graphene oxide on surface of photoresist and substrate material |
| CN114214690B (en) * | 2021-12-27 | 2023-09-26 | 宁波南大光电材料有限公司 | Electroplating method for plating graphene oxide on surface of photoresist and substrate material |
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