CN103682352A - Lithium ion secondary battery, positive electrode material of battery, and preparation method of material - Google Patents
Lithium ion secondary battery, positive electrode material of battery, and preparation method of material Download PDFInfo
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- CN103682352A CN103682352A CN201210330279.0A CN201210330279A CN103682352A CN 103682352 A CN103682352 A CN 103682352A CN 201210330279 A CN201210330279 A CN 201210330279A CN 103682352 A CN103682352 A CN 103682352A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention provides a lithium ion secondary battery, a positive electrode material of the battery, and a preparation method of the material. The positive electrode material of the lithium ion secondary battery comprises graphene and nanometer sulfur particles which are loaded on the surface of the graphene. The graphene oxide or graphene, nanometer sulfur powder, a surface active agent and a reducing agent are adopted as raw materials, and after being mixed, the raw materials perform hydrothermal reaction to obtain the positive electrode material of the lithium ion secondary battery. The electronic conductivity of the positive electrode material is improved by virtue of the excellent conductivity of the graphene, and the dissolution of polysulfide ions can be alleviated through the unique two-dimensional structure of the graphene, so that the gradual attenuation of the electric capacity can be inhibited, and the cycling property of the battery can be improved. The experimental result shows that the primary discharging capacity of the positive electrode active material can reach 1100mAh/g under 0.1C, the capacity can be maintained at 800mAh/g after the battery is cycled for 50 times, the discharging capacity can be maintained at 450mAh/g under 2C, and the rate performance of the battery is excellent.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, relate in particular to lithium ion secondary battery anode material, its preparation method and lithium rechargeable battery.
Background technology
The fast development in the fields such as current communication, portable electric appts, electric automobile and space technology, the performance of battery has been proposed to more and more higher requirement, and development has high-energy-density, low cost and eco-friendly new type lithium ion secondary cell and has very important significance.
In lithium rechargeable battery system, the performance of positive electrode is the bottleneck of restriction battery development always.Traditional transition metal oxide base anode material is as LiCoO
2, LiNiO
2, LiMn
2o
4deng the restriction due to its theoretical lithium storage content, make take its positive electrode that is lithium rechargeable battery to be difficult to make lithium battery to make a breakthrough in energy density.In order to improve the performance of lithium rechargeable battery, prior art has developed lithium-sulfur cell, it belongs to serondary lithium battery system, by elemental sulfur (theoretical specific capacity is 1675mAh/g), lithium metal (theoretical specific capacity is 3860mAh/g) and organic electrolyte, formed, there is specific energy high (theoretical value is 2600Wh/kg), low, the environment amenable feature of cost, can meet market to chemical power source lightweight, miniaturization, low cost and nontoxic requirement.But there are following 3 problems in lithium-sulfur cell: (1) elemental sulfur is non-conductive in room temperature, so lithium-sulfur cell active material utilization is very low and chemical property is not good; (2) many lithium sulfides that lithium-sulfur cell charge and discharge process produces are soluble in organic electrolyte, and the active material of electrode is reduced gradually, cause the capacity of battery progressively to be decayed, cycle performance variation; (3) in cyclic process, in lithium-sulfur cell, the volume deformation of sulfur electrode, up to 22%, may make the inner micro-crack that produces of sulfur electrode, and the existence of this micro-crack has destroyed the globality of electrode, finally aggravates the capacity attenuation of lithium-sulfur cell.
The above-mentioned shortcoming existing in order to overcome lithium-sulfur cell, prior art discloses multiple employing porous carbon or mesoporous carbon improving one's methods to sulphur positive electrode.As adopted ordered mesopore carbon CMK-3(pitch of holes 6.5nm as Ji etc., aperture 3-4nm) as conductive phase, during the sulphur infiltration of heat fused is mesoporous, obtaining sulfur content is the CMK-3/S composite material of 70wt%, 20 Reversible Cycle specific capacities of composite material are 800mAh/g(Ji X L, Lee K T, Nazar L F.Nature Mater., 2009,8:500 ~ 506.); The method of the use heating such as Lai is by the compound S/HPC compound that obtains of the porous carbon of sulphur and a kind of high-specific surface area, and because porous carbon has high specific area, sulphur can fully contact with it, for electrochemical process provides necessary electric transmission approach.The specific area of porous carbon is larger, more with sulphur contact-making surface, to improving the performance more favourable (Lai C, Gao X P, Zhang B, Yan T T, Zhou Z.J..Phys.Chem.C, 2009,113:4712 ~ 4716.) of battery; The employings such as Liang have the mesoporous carbon in two-stage aperture as conductive phase, and this mesoporous carbon has the hole of two kinds of sizes of 7.3nm and 2nm.While there is the hole of two kinds of sizes in conductive phase, micro hole is wherein as the memory space of sulphur, macropore is as the holder that is dissolved in the polysulfide of electrolyte, such structure is conducive to polysulfide to be limited in the anodal inside of sulphur and can not diffuse out electrode, thereby can not cause the loss of active material and the corrosion of anticathode, can obviously improve the cyclical stability of sulfur electrode, the composite material that sulfur content is 11.7wt% reversible specific capacity after 50 circulations is 780mAh/g.But the cycle performance of lithium-sulfur cell prepared by the positive electrode that this mesoporous carbon or porous carbon materials obtain is poor.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion secondary battery anode material, its preparation method and lithium rechargeable battery, lithium ion secondary battery anode material provided by the invention has good chemical property, higher capacity and higher cycle performance simultaneously.
The invention provides a kind of lithium ion secondary battery anode material, comprise Graphene;
Be carried on the nano-sulfur particles on described Graphene surface.
Preferably, the mass ratio of described Graphene and nano-sulfur particles is 1:(1 ~ 5).
Preferably, the diameter of described Graphene is 1 μ m ~ 50 μ m.
Preferably, the size of described nano-sulfur particles is 5nm ~ 100nm.
The preparation method who the invention provides a kind of lithium ion secondary battery anode material, comprises the following steps:
Graphite oxide aqueous solution, surfactant, reducing agent and nano-sulfur powder are mixed, or graphene aqueous solution, surfactant and nano-sulfur powder are mixed, obtain mixed solution;
Described mixed solution is carried out to hydro-thermal reaction, obtain lithium ion secondary battery anode material.
Preferably, the mass concentration of described graphene oxide or graphene aqueous solution is 1g/L ~ 50g/L.
Preferably, described surfactant is nonionic surface active agent.
Preferably, the mass ratio of described graphene oxide, surfactant, reducing agent and nano-sulfur powder is 1:(0.001 ~ 0.005): (0.50 ~ 2): (1 ~ 3);
The mass ratio of described Graphene, surfactant and nano-sulfur powder is 1:(0.001 ~ 0.005): (1 ~ 5).
Preferably, the temperature of described hydro-thermal reaction is 100 ℃ ~ 200 ℃;
The time of described hydro-thermal reaction is 6h ~ 24h.
The invention provides a kind of lithium rechargeable battery, it is characterized in that, the anodal lithium ion secondary battery anode material of being prepared by the lithium ion secondary battery anode material described in technique scheme or the preparation method described in technique scheme forms.
The invention provides a kind of lithium ion secondary battery anode material, its preparation method and lithium rechargeable battery, lithium ion secondary battery anode material provided by the invention comprises Graphene and is carried on the nano-sulfur particles on described Graphene surface.The conductivity of Graphene excellence and unique two-dimensional structure make it than nano particle or nano wire etc., have outstanding advantage improving on material electrochemical performance, its excellent electric conductivity is given the electron conductivity of combination electrode material excellence, its unique two-dimensional structure can effectively be coated active material, it is nano-sulfur particles, alleviate the dissolving of many sulphions, thereby guaranteed the amount of electrode active material, suppressed the progressively decay of battery capacity, there is good cycle performance; Its unique flexible structure can overcome the bulk effect of sulphur, can not make the inside of sulfur electrode produce micro-crack, thereby keep the integrality of electrode, has improved cycle performance.Experimental result shows, under positive electrode 0.1C provided by the invention, discharge capacity reaches 1100mAh/g first, and 50 Capacitance reserves that circulate are 800mAh/g, and 2C discharge capacity remains on 450mAh/g, and high rate performance is good.
Preparation method provided by the invention be take sulphur, graphene oxide, surfactant and reducing agent as raw material, or take sulphur, Graphene and surfactant as raw material, by hydro thermal method one-step synthesis lithium ion secondary battery anode material, method reaction temperature provided by the invention and, can not damage raw material; And the size and dimension that can control nano-sulfur particles by kind and the consumption of adjustment form surface-active agent, make lithium ion secondary battery anode material provided by the invention there is the controllability of good size and dimension.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the lithium ion secondary battery anode material that obtains of the embodiment of the present invention 1;
Fig. 2 is the thermogravimetric analysis figure of the lithium ion secondary battery anode material that obtains of the embodiment of the present invention 1;
Fig. 3 is the cyclic curve of the lithium ion secondary battery anode material that obtains of the embodiment of the present invention 2 under 0.1C multiplying power;
Fig. 4 is the cyclic curve of the lithium ion secondary battery anode material that obtains of the embodiment of the present invention 2 under different multiplying.
Embodiment
The invention provides a kind of lithium ion secondary battery anode material, comprise Graphene;
Be carried on the nano-sulfur particles on described Graphene surface.
Lithium ion secondary battery anode material provided by the invention comprises Graphene, at the area load of described Graphene, has nano-sulfur particles.The conductivity of Graphene excellence and unique two-dimensional structure make it than nano materials such as nano particle or nano wires, on material electrochemical performance, there is outstanding advantage improving, its excellent electric conductivity is given the electron conductivity of combination electrode material excellence, its unique two-dimensional structure can effectively be coated active material, alleviate the dissolving of many sulphions, thereby guaranteed the amount of electrode active material, suppressed the progressively decay of battery capacity, there is good cycle performance; Its unique flexible structure can overcome the bulk effect of sulphur, can not make the inside of sulfur electrode produce micro-crack, thereby keep the integrality of electrode, thereby can improve the cycle performance of battery.
Lithium ion secondary battery anode material provided by the invention comprises Graphene, in the present invention, described Graphene finally obtains after being reduced by graphene oxide in preparation process, or directly take Graphene and prepare lithium ion secondary battery anode material as raw material.In the present invention, described graphene oxide is preferably standby according to Hummers legal system, if directly take Graphene as raw material, described Graphene can be the Graphene commodity that Ningbo Mo Xi Science and Technology Ltd. provides.
Lithium ion secondary battery anode material provided by the invention comprises Graphene, Graphene has excellent conductivity and unique two-dimensional structure, its unique two-dimensional structure can be coated active material effectively, alleviate the dissolving of many sulphions, thereby can not cause the minimizing of electroactive material because of the dissolving of a large amount of many sulphions and affect battery capacity, make lithium ion secondary battery anode material provided by the invention there is good cycle performance; And the flexible structure of Graphene uniqueness can overcome the bulk effect of sulphur, thereby can not make due to the volumetric expansion of sulphur the inner micro-crack that produces of sulfur electrode, the integrality of electrode is guaranteed, thereby makes lithium ion secondary battery anode material provided by the invention there is higher capacity.In the present invention, the diameter of described Graphene is preferably 1 μ m ~ 50 μ m.
Lithium ion secondary battery anode material provided by the invention comprises nano-sulfur particles, and described nano-sulfur particles is carried on the surface of described Graphene.Sulphur simple substance has higher theoretical specific capacity, it is carried on the surface of Graphene, because the good Electronic Performance of Graphene and two-dimensional structure have overcome the defect of sulphur in sulphur lithium battery in prior art, make lithium ion secondary battery anode material provided by the invention there is good chemical property.In the present invention, the mass ratio of described Graphene and described nano-sulfur particles is preferably 1:(1 ~ 5); The size of described nano-sulfur particles is preferably 5nm ~ 100nm, more preferably 10nm ~ 90nm.
The invention provides a kind of lithium ion secondary battery anode material, comprise Graphene and the nano-sulfur particles that is carried on described Graphene surface.Because the existence of Graphene has overcome sulphur in prior art, as the defect of positive electrode, the excellent properties of sulphur itself is retained, thereby make lithium ion secondary battery anode material provided by the invention there is higher chemical property and cycle performance.Experimental result shows, the button cell that uses lithium particle secondary battery positive electrode material assembling provided by the invention, under 0.1C, discharge capacity reaches 1100mAh/g first, and 50 Capacitance reserves that circulate are 800mAh/g, 2C discharge capacity remains on 450mAh/g, and high rate performance is good.
The preparation method who the invention provides a kind of lithium ion secondary battery anode material, comprises the following steps:
Graphite oxide aqueous solution, surfactant, reducing agent and nano-sulfur powder are mixed, or graphene aqueous solution, surfactant and nano-sulfur powder are mixed, obtain mixed solution;
Described mixed solution is carried out to hydro-thermal reaction, obtain lithium ion secondary battery anode material.
First-selection of the present invention mixes the aqueous solution of graphene oxide, surfactant, reducing agent and sulphur powder, or the aqueous solution of Graphene, surfactant and sulphur powder are mixed, and obtains mixed solution.
The present invention can be take graphene oxide as raw material, also can directly take Graphene as raw material, prepares lithium ion secondary battery anode material.If take graphene oxide as raw material, the present invention says that graphite oxide aqueous solution, surfactant, reducing agent and nano-sulfur powder mix, and obtain mixed solution; Described graphene oxide is preferably prepared according to the Hummers method described in technique scheme, obtains after graphene oxide, and the present invention obtains its preparation the aqueous solution of graphene oxide; If take Graphene as raw material, the present invention can adopt commercially available Graphene commodity, as the Graphene commodity that Ningbo Mo Xi Science and Technology Ltd. provides, described Graphene is prepared and is obtained graphene aqueous solution; The present invention mixes described graphene aqueous solution, surfactant and nano-sulfur powder, obtains mixed solution.The present invention does not have special restriction to the compound method of described graphene oxide or graphene aqueous solution, adopts the compound method of the aqueous solution well known to those skilled in the art.In the present invention, the mass concentration of described graphene oxide or graphene aqueous solution is preferably 1g/L ~ 50g/L, more preferably 2g/L ~ 40g/L.
Obtain after graphene oxide or graphene aqueous solution, the present invention mixes described graphite oxide aqueous solution with surfactant, reducing agent and nano-sulfur powder, or graphene aqueous solution is mixed with surfactant and nano-sulfur powder, preferably carry out ultrasonic, it is mixed, obtain mixed solution.In the present invention, described surfactant is preferably nonionic surface active agent, more preferably Qu Latong TX-100 or polyethylene glycol; Described reducing agent is preferably hydrazine hydrate, sodium borohydride, lithium aluminium hydride reduction, ascorbic acid or glucose, more preferably sodium borohydride or glucose; The mass ratio of described graphene oxide, surfactant, reducing agent and nano-sulfur powder is preferably 1:(0.001 ~ 0.005): (0.50 ~ 2): (1 ~ 3); The mass ratio of described Graphene, surfactant and nano-sulfur powder is preferably 1:(0.001 ~ 0.005): (1 ~ 5); The described ultrasonic time is preferably 5min ~ 30min, more preferably 10min ~ 25min.
Obtain after mixed solution, the present invention carries out hydro-thermal reaction by described mixed solution, obtains lithium ion secondary battery anode material.When take graphene oxide during as raw material, in hydrothermal reaction process, graphene oxide, under the reduction of reducing agent, becomes Graphene, has had higher conductivity; Under the effect of surfactant, sulphur powder is carried on the surface of the Graphene obtaining simultaneously, and growth forms nano-sulfur particles, and, due to the effect of surfactant, by changing kind and its consumption of surfactant, realized the adjusting to Graphene nano surface sulfur granules size and dimension.In addition, the mild condition of hydro-thermal reaction, can not cause damage to the performance of reaction raw materials and the product obtaining.In the present invention, the temperature of described hydro-thermal reaction is preferably 100 ℃ ~ 200 ℃; The time of described hydro-thermal reaction is preferably 6h ~ 24h.
Complete after hydro-thermal reaction, the present invention preferably cleans the product obtaining, and then obtains lithium ion secondary battery anode material after being dried.The present invention preferably adopts deionized water to clean described product, until clean up; Described being dried is preferably vacuumize, freeze drying or sprays dry, the present invention does not have special restriction to described vacuumize, freeze drying or spray-dired method, adopts vacuumize well known to those skilled in the art, freeze drying or spray-dired technical scheme.
Obtain after lithium ion secondary battery anode material, the sign that the present invention has carried out performance to it, detailed process is as follows:
Take lithium ion secondary battery anode material provided by the invention as anodal, adopt Cellgard2000 barrier film, lithium trifluoromethanesulp,onylimide/dioxolane-glycol dimethyl ether that the molar concentration of take is 1mol/L is electrolyte solution, take lithium paper tinsel as negative pole, in argon gas atmosphere glove box, assemble simulated battery, adopt LANDCT2001A-5V/1mA type battery test system to carry out constant current charge-discharge test, voltage window is 1.0V～3V.Result shows, lithium ion secondary battery anode material provided by the invention has higher capacitance, and high rate performance is good.
The invention provides a kind of lithium rechargeable battery, it is characterized in that, the anodal lithium ion secondary battery anode material of being prepared by the lithium ion secondary battery anode material described in technique scheme or the preparation method described in technique scheme forms.It is anodal that the lithium ion secondary battery anode material that prepared by preparation method described in lithium ion secondary battery anode material that technique scheme provides or technique scheme is take in the present invention, adopt the technical scheme of assembling lithium rechargeable battery well known to those skilled in the art, assembling obtains lithium rechargeable battery.
The invention provides a kind of lithium ion secondary battery anode material, its preparation method and lithium rechargeable battery, lithium ion secondary battery anode material provided by the invention comprises Graphene and is carried on the nano-sulfur particles on described Graphene surface.The conductivity of Graphene excellence and unique two-dimensional structure make it than nano particle or nano wire etc., have outstanding advantage improving on material electrochemical performance, its excellent electric conductivity is given the electron conductivity of combination electrode excellence, its unique two-dimensional structure can effectively be coated active material, alleviate the dissolving of many sulphions, thereby guaranteed the amount of electrode active material, suppress the progressively decay of battery capacity, there is good cycle performance; Its unique flexible structure can overcome the bulk effect of sulphur, can not make the inside of sulfur electrode produce micro-crack, thereby keep the integrality of electrode, has improved cycle performance.Experimental result shows, under lithium ion secondary battery anode material 0.1C provided by the invention, discharge capacity reaches 1100mAh/g first, and 50 Capacitance reserves that circulate are 800mAh/g, and 2C discharge capacity remains on 450mAh/g, and high rate performance is good.
Preparation method provided by the invention be take sulphur, graphene oxide, surfactant and reducing agent as raw material, or take sulphur, Graphene and surfactant as raw material, by hydro thermal method one-step synthesis lithium ion secondary battery anode material, method reaction temperature provided by the invention and, can not damage raw material; And the size and dimension that can control nano-sulfur particles by kind and the consumption of adjustment form surface-active agent, make lithium ion secondary battery anode material provided by the invention there is the controllability of good size and dimension.
In order to further illustrate the present invention, below in conjunction with embodiment, lithium ion secondary battery anode material provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as to limiting the scope of the present invention.
According to graphene oxide: surfactant: reducing agent: the mass ratio of sulphur powder=1:0.001:0.5:1, the graphite oxide aqueous solution that preparation mass concentration is 10g/L.In the graphite oxide aqueous solution that is 10g/L to 100mL mass concentration, add 0.01g song to draw logical TX-100,0.5g sodium borohydride and 1g nano-sulfur powder, ultrasonic 10 minutes, obtain uniform mixed solution; Described mixed solution is placed in to hydro-thermal tank, in the air dry oven of 100 ℃, reacts after 8 hours, obtain product.Then will obtain product and clean up with deionized water, the dry lithium ion secondary battery anode material that obtains under vacuum condition.
The present invention carries out ESEM scanning analysis to the lithium ion secondary battery anode material obtaining, obtained its shape appearance figure, result as shown in Figure 1, Fig. 1 is the SEM figure that the embodiment of the present invention 1 obtains lithium ion secondary battery anode material, as seen from Figure 1, nano-sulfur particles size is 100nm left and right, and uniform load is on the surface of graphene film, close contact between graphene film and nano-sulfur particles is conducive to improve the conductivity of positive electrode, and Graphene is to being conducive to suppress the dissolving of polysulfide to the load of sulphur.
The present invention carries out thermogravimetric analysis to the lithium ion secondary battery anode material obtaining, result as shown in Figure 2, Fig. 2 is the thermogravimetric analysis figure of the lithium ion secondary battery anode material that obtains of the embodiment of the present invention 1, as seen from Figure 2, in the lithium ion secondary battery anode material that prepared by the present embodiment, the content of element sulphur is about 80%.
Embodiment 2
The lithium ion secondary battery anode material that embodiment 1 example is obtained with conductive agent Super P, binding agent Kynoar in mass ratio for the ratio of 80:10:10 mixes in nitrogen methyl pyrrolidone, and the mixed solution obtaining is coated on aluminium foil, coating thickness is 30 μ m, after the aluminium foil that is coated with mixed solution is dried at 80 ℃, obtains positive plate.Take lithium sheet as negative pole, and microporous polypropylene film is barrier film, the LiN (CF that molar concentration is 1mol/L
3sO
2)
2non-aqueous solution (solvent is the mixed solvent of isopyknic DOX and dipropyl carbonate) is electrolyte, obtains lithium rechargeable battery with the positive plate assembling obtaining.
The present invention has investigated the situation that the lithium ion secondary battery anode material that obtains discharges and recharges, result as shown in Figure 3 and Figure 4, the lithium ion secondary battery anode material that the embodiment of the present invention 2 obtains is first charge-discharge curve under 0.1C multiplying power, as seen from Figure 3, lithium ion secondary battery anode material provided by the invention first discharge capacity reaches 1100mAh/g, and 50 Capacitance reserves that circulate are 800mAh/g.Fig. 4 is the cyclic curve of the lithium ion secondary battery anode material that obtains of the embodiment of the present invention 2 under different multiplying, and as seen from Figure 4, after 2C circulation 5 times, its capacity still remains on 450mAh/g, and high rate performance is good.
Embodiment 3
According to graphene oxide: surfactant: reducing agent: the mass ratio of sulphur powder=1:0.005:2:5, the graphite oxide aqueous solution that preparation mass concentration is 1g/L.In the graphite oxide aqueous solution that is 1g/L to 100mL mass concentration, add 0.0005g song to draw logical TX-100,0.2g glucose and 0.5g nano-sulfur powder, ultrasonic 10 minutes, obtain uniform mixed solution; Described mixed solution is placed in to hydro-thermal tank, in the air dry oven of 200 ℃, reacts after 6 hours, obtain product.Then will obtain product and clean up with deionized water, the dry lithium ion secondary battery anode material that obtains under vacuum condition.
The present invention has investigated the chemical property of the lithium ion secondary battery anode material obtaining, result shows, lithium ion secondary battery anode material provided by the invention, 0.1C initial discharge capacity is 1000mAh/g, irreversible capacity is almost 0 first, 50 the later capacity that circulate reach 700mAh/g, good performance in also showing under high magnification.
Embodiment 4
According to graphene oxide: surfactant: reducing agent: the mass ratio of sulphur powder=1:0.002:1:3, the graphite oxide aqueous solution that preparation mass concentration is 50g/L.In the graphite oxide aqueous solution that is 50g/L to 10mL mass concentration, add 0.001g song to draw logical TX-100,0.5g ascorbic acid and 1.5g nano-sulfur powder, ultrasonic 10 minutes, obtain uniform mixed solution; Described mixed solution is placed in the air dry oven of 180 ℃, reacts after 24 hours, obtain product.Then the product obtaining is cleaned up with deionized water, after being dried, obtain lithium ion secondary battery anode material under vacuum condition.
The present invention has investigated the chemical property of the lithium ion secondary battery anode material obtaining, result shows, lithium ion secondary battery anode material provided by the invention, 0.1C initial discharge capacity is 1000mAh/g, irreversible capacity is almost 0 first, 50 the later capacity that circulate reach 780mAh/g, good performance in also showing under high magnification.
Embodiment 5
According to graphene oxide: surfactant: reducing agent: the mass ratio of sulphur powder=1:0.003:1.5:4, the graphite oxide aqueous solution that preparation mass concentration is 20g/L.In the graphite oxide aqueous solution that is 20g/L to 100mL mass concentration, add 0.006g song to draw logical TX-100,3g ascorbic acid and 8g nano-sulfur powder, ultrasonic 10 minutes, obtain mixed solution; Described mixed solution is placed in the air dry oven of 150 ℃, reacts after 12 hours, obtain product.Then the product obtaining is cleaned up with deionized water, after being dried, obtain lithium ion secondary battery anode material under vacuum condition.
The present invention has investigated the performance of the lithium ion secondary battery anode material that the present embodiment obtains, and result shows, its initial discharge capacity is 1080mAh/g, and irreversible capacity is almost 0 first, and the capacity after 50 times that circulate reach 800mAh/g.
As can be seen from the above embodiments, the invention provides a kind of lithium ion secondary battery anode material, its preparation method and lithium rechargeable battery, lithium ion secondary battery anode material provided by the invention comprises Graphene and is carried on the nano-sulfur particles on described Graphene surface.The conductivity of Graphene excellence and unique two-dimensional structure make it than nano particle or nano wire etc., have outstanding advantage improving on material electrochemical performance, its excellent electric conductivity is given the electron conductivity of combination electrode excellence, its unique two-dimensional structure can effectively be coated active material, alleviate the dissolving of many sulphions, thereby guaranteed the amount of electrode active material, suppress the progressively decay of battery capacity, there is good cycle performance; Its unique flexible structure can overcome the bulk effect of sulphur, can not make the inside of sulfur electrode produce micro-crack, thereby keep the integrality of electrode, has improved cycle performance.Experimental result shows, under this positive electrode 0.1C, discharge capacity reaches 1100mAh/g first, and 50 Capacitance reserves that circulate are 800mAh/g, and 2C discharge capacity remains on 450mAh/g, and high rate performance is good.
Preparation method provided by the invention be take sulphur, graphene oxide, surfactant and reducing agent as raw material, or take sulphur, Graphene and surfactant as raw material, by hydro thermal method one-step synthesis lithium ion secondary battery anode material, method reaction temperature provided by the invention and, can not damage raw material; And the size and dimension that can control nano-sulfur particles by kind and the consumption of adjustment form surface-active agent, make lithium ion secondary battery anode material provided by the invention there is the controllability of good size and dimension.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a lithium ion secondary battery anode material, comprises Graphene;
Be carried on the nano-sulfur particles on described Graphene surface.
2. lithium ion secondary battery anode material according to claim 1, is characterized in that, the mass ratio of described Graphene and nano-sulfur particles is 1:(1 ~ 5).
3. lithium ion secondary battery anode material according to claim 1, is characterized in that, the diameter of described Graphene is 1 μ m ~ 50 μ m.
4. lithium ion secondary battery anode material according to claim 1, is characterized in that, the size of described nano-sulfur particles is 5nm ~ 100nm.
5. a preparation method for lithium ion secondary battery anode material, comprises the following steps:
Graphite oxide aqueous solution, surfactant, reducing agent and nano-sulfur powder are mixed, or graphene aqueous solution, surfactant and nano-sulfur powder are mixed, obtain mixed solution;
Described mixed solution is carried out to hydro-thermal reaction, obtain lithium ion secondary battery anode material.
6. preparation method according to claim 5, is characterized in that, the mass concentration of described graphene oxide or graphene aqueous solution is 1g/L ~ 50g/L.
7. preparation method according to claim 5, is characterized in that, described surfactant is nonionic surface active agent.
8. preparation method according to claim 5, is characterized in that, the mass ratio of described graphene oxide, surfactant, reducing agent and nano-sulfur powder is 1:(0.001 ~ 0.005): (0.50 ~ 2): (1 ~ 5);
The mass ratio of described Graphene, surfactant and nano-sulfur powder is 1:(0.001 ~ 0.005): (1 ~ 5).
9. preparation method according to claim 5, is characterized in that, the temperature of described hydro-thermal reaction is 100 ℃ ~ 200 ℃;
The time of described hydro-thermal reaction is 6h ~ 24h.
10. a lithium rechargeable battery, is characterized in that, the anodal lithium ion secondary battery anode material of being prepared by the lithium ion secondary battery anode material described in claim 1 ~ 4 any one or the preparation method described in claim 5 ~ 9 any one forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210330279.0A CN103682352A (en) | 2012-09-07 | 2012-09-07 | Lithium ion secondary battery, positive electrode material of battery, and preparation method of material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN104051735A (en) * | 2014-06-27 | 2014-09-17 | 青岛大学 | Preparation method and application of elemental-sulfur-loaded spherical MoS2/graphene nano composite material |
| CN104953102A (en) * | 2015-06-29 | 2015-09-30 | 北京理工大学 | Preparation method of lithium-sulfur battery applicable to industrialized production |
| CN106532016A (en) * | 2016-12-28 | 2017-03-22 | 西北工业大学 | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
| CN108232132A (en) * | 2017-12-13 | 2018-06-29 | 中国科学院福建物质结构研究所 | Cell negative electrode material and its preparation and application |
| CN109205594A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of preparation method and applications of graphene conductive microballoon |
| CN111024681A (en) * | 2019-12-17 | 2020-04-17 | 国联汽车动力电池研究院有限责任公司 | Ternary lithium ion battery positive pole piece analysis method |
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| CN102185147A (en) * | 2011-04-15 | 2011-09-14 | 南京师范大学 | Nano iron phosphate hollow sphere/graphene composite material and preparation method thereof |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN102522542A (en) * | 2011-12-14 | 2012-06-27 | 上海交通大学 | Elemental sulfur composite material containing graphene and preparation method thereof |
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| CN102185147A (en) * | 2011-04-15 | 2011-09-14 | 南京师范大学 | Nano iron phosphate hollow sphere/graphene composite material and preparation method thereof |
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| CN104051735A (en) * | 2014-06-27 | 2014-09-17 | 青岛大学 | Preparation method and application of elemental-sulfur-loaded spherical MoS2/graphene nano composite material |
| CN104953102A (en) * | 2015-06-29 | 2015-09-30 | 北京理工大学 | Preparation method of lithium-sulfur battery applicable to industrialized production |
| CN106532016A (en) * | 2016-12-28 | 2017-03-22 | 西北工业大学 | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
| CN106532016B (en) * | 2016-12-28 | 2019-03-15 | 西北工业大学 | A kind of lithium-sulfur battery composite cathode material and preparation method thereof |
| CN109205594A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of preparation method and applications of graphene conductive microballoon |
| CN108232132A (en) * | 2017-12-13 | 2018-06-29 | 中国科学院福建物质结构研究所 | Cell negative electrode material and its preparation and application |
| CN108232132B (en) * | 2017-12-13 | 2020-12-29 | 中国科学院福建物质结构研究所 | Battery cathode material and preparation and application thereof |
| CN111024681A (en) * | 2019-12-17 | 2020-04-17 | 国联汽车动力电池研究院有限责任公司 | Ternary lithium ion battery positive pole piece analysis method |
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