CN103117400A - Secondary lithium-air battery cathode catalyst - Google Patents
Secondary lithium-air battery cathode catalyst Download PDFInfo
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Abstract
The invention discloses a secondary lithium-air battery cathode catalyst. The catalyst is a carbon material doped with exotic atoms, wherein the exotic atoms are phosphorus and a transition metal element; the carbon material is a porous carbon, graphene or carbon nano-tube; the molar ratio of the exotic atoms to the carbon material is 1:(19-99); and the molar ratio of phosphorus to the transition metal element in the exotic atoms is (1-4):1. The secondary lithium-air battery cathode catalyst has double-function property, can significantly reduce battery charge and discharge polarization, achieves high charge and discharge capacity, excellent charge and discharge magnification and long cycle life, can obviously reduce the production cost, and at the same time has excellent catalytic efficiency. A secondary lithium-air battery containing the catalyst has the advantage of high energy density, and is applicable to the field of various mobile electronic equipment and electric batteries.
Description
Technical field
The present invention relates to a kind of battery material, be specifically related to a kind of secondary lithium-air battery cathod catalyst, belong to high-performance chemical power supply eelctro-catalyst field.
Background technology
Due to the fast-developing and modern people in the fields such as space technology, mobile communication, guided missile, the Aero-Space care to energy crisis, environmental protection, the research of high energy-storage battery, exploitation have caused people's extensive concern.Because lithium is that in all metallic elements, quality is minimum, electrode potential is minimum, so the battery that is comprised of lithium has the characteristics such as open circuit voltage is high, specific discharge capacity is large, having substituted rapidly NI-G, Ni-MH battery recent years becomes most popular high-energy battery.
The secondary lithium-air battery is a kind of battery take oxygen as positive electrode active materials, take lithium metal as negative active core-shell material, also claims by " lithium metal fuel cell ".Because oxygen derives from air, inexhaustible, nexhaustible, thereby the secondary lithium-air battery has, and cost is low, environment amenable advantage.The open circuit voltage of secondary lithium-air battery is about 3.0 V, is 3 times of hydrogen-air fuel cell; Because oxygen does not need to be stored in inside battery, its theoretical energy density is up to 5.21 kWh/kg (oxygenous) or 11.14 kWh/kg (oxygen-free gas), far above the theoretical energy density (200-250 Wh/kg) of traditional lithium ion battery, its performance can compare favourably with gasoline (12.22 kWh/kg).Therefore, the secondary lithium-air battery has broad application prospects in fields such as portable type electronic product and communication apparatus as high-energy-density power supply of new generation, especially can satisfy the requirement of the high-energy-density of electric car power supply.
At present, the secondary lithium-air battery is in quick development in the world.In secondary lithium-air battery charge and discharge process, as the air electrode (being oxygen electrode) of negative electrode, the chemical property of battery there is decisive influence.The place of metal oxide decomposition reaction occurs in air electrode when when being the discharge of secondary lithium-air battery, oxygen reduction reaction and charging occuring, have typical gas-liquid-solid phase reaction boundary zone, in course of reaction due to the oxygen electrochemical reducting reaction of air electrode slowly and Li
2O
2/ Li
2The activation energy of O electrochemical oxidation precipitated oxygen is high and caused that battery charging and discharging polarization is large, efficiency for charge-discharge is low and cycle performance is poor.
Need to overcome these shortcomings, the use of catalyst is crucial, cathod catalyst is as the important component part of lithium-air battery, for the lithium peroxide in the lithium-air battery charge and discharge process forms and decomposition provides catalytic center, not only affect charge and discharge potential, the charge/discharge capacity of secondary lithium-air battery but also affect the cyclicity of battery, it can promote Li in charging process
2O
2/ Li
2The decomposition of O improves cycle efficieny.
The people such as Abraham use carbon to carry cobalt phthalein mountain valley with clumps of trees and bamboo macrocyclic compound and are assembled into lithium-air battery as cathod catalyst, make the overpotential of battery reduce 0.65V, and battery table reveals good cycle efficieny, charge and discharge cycles three circles, and the battery capacity decay is very little; But the macrocyclic compound catalyst that phthalocyanine and transition-metal coordination generate, complicated process of preparation, productive rate is low, and the cost of material of synthetic macrocyclic compound is high, synthetic route is long, side reaction is many, thereby has improved greatly the preparation cost (K.M.Abraham of catalyst; Z.Jiang A Polymer Electrolyte ?Based Rechargeable Lithium/Oxygen Battery. J.Electrochem.Soc. 1996 143:1).
The people such as Yang have prepared the noble metal nano catalyst Pt
0.5Au
0.5/ C is applied in lithium-air battery, result of study shows, this catalyst has the economic benefits and social benefits catalytic action, both promoted the discharge voltage (than the high 0.2V of pure carbon left and right) of battery, reduced again the charging voltage (having reduced about 0.6V than pure carbon) of battery, the remarkable efficiency for charge-discharge that has promoted battery; Although the noble metal such as Pt, Au has shown excellent catalytic effect, because its expensive price and rare resource are unfavorable for practical application (S.H.Yang et al. Platinum Gold Nanoparticles:A Highly Active Bifunctional Electrocatalyst for Rechargeable Lithium Air Batteries. J.Am.Chem.Soc. 2010 132:12170).
Peter G.Bruce etc. has studied the electrocatalysis characteristic of dissimilar transition metal oxide, finds that electrolytic oxidation manganese and cobalt oxide are having discharge capacity, cycle performance and electrocatalysis characteristic (Peter G.Bruce.et al. An O preferably
2Cathode for rechargeable lithium batteries:The effect of a catalyst. Journal of Power Sources 2007 174:1177); The employing redox such as Jiaxin Li have been prepared carbon and have been carried the manganese oxide electrocatalysis material, and its discharge capacity surpasses 1800mAh/g, and discharge platform is higher than 2.8V, and charging platform is lower than 3.8V, battery polarization decrease (Jiaxin Li; Ning Wang; Yi Zhao; Yunhai Ding; Lunhui Guan. MnO
2Nanoflakes coated on multi-walled carbon nanotubes for rechargeable lithium-air batteries. Electrochemistry Communications 2011 13:698).When using transition metal oxide as eelctro-catalyst, its lithium-air battery has that discharge capacity is high, good cycle, the feature of electrocatalysis characteristic preferably, but the conductivity of transition metal oxide is bad, and reaction easily is terminated, and can not give play to stable electrocatalysis characteristic.
Thereby, need that research and development are more efficiently, secondary lithium-air battery cathod catalyst to be promoting in discharge process separating out of oxygen in oxygen reduction and charging process cheaply, thereby improve the performance of secondary lithium-air battery.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of secondary lithium-air battery cathod catalyst, with charge and discharge potential, increase charge/discharge capacity, the raising cycle efficieny that reduces battery.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of secondary lithium-air battery cathod catalyst, this catalyst are exotic atom doping carbon material, and wherein, exotic atom is phosphorus and transition metal; Material with carbon element is porous carbon, Graphene or multi-walled carbon nano-tubes; The mol ratio of exotic atom and carbon 1: 19～99; The mol ratio 1～4: 1 of phosphorus and transition metal in exotic atom.
In technique scheme, described transition metal is one or several in Fe, Co, Ni, Cr, Mn.
In technique scheme, the aperture of described porous carbon is 0.1～200nm; The thickness of Graphene is 0.4～10nm; The diameter of multi-walled carbon nano-tubes is 1～100nm.
In preferred technical scheme, the mol ratio of exotic atom and material with carbon element is 1:19; In exotic atom, the mol ratio of phosphorus and transition metal is 4:1.
In the present invention, the mode of phosphorus, transition metal element doped material with carbon element is in-situ doped method, also can be the ex situ doping method.The catalyst for preparing can effectively promote the generation of oxygen reduction reaction when battery discharge, simultaneously, can effectively promote again the generation of oxygen evolution reaction when battery charges, and is bifunctional catalyst.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1, the invention provides a kind of secondary lithium-air battery cathod catalyst, have difunctional character, can significantly reduce the charge and discharge polarization of battery, and obtain high charge and discharge capacity, excellent charge and discharge multiplying power and long cycle life.
2, the present invention's catalyst agent of being made by phosphorus, transition metal element doped material with carbon element can obviously reduce production costs, and has simultaneously excellent catalytic efficiency.
Description of drawings
Fig. 1 is the microscopic appearance figure of catalyst in embodiment 1.
Fig. 2 is the elementary analysis figure of catalyst in embodiment 1.
Fig. 3 is N in embodiment 1
2The adsorption desorption curve chart.
Fig. 4 is the micropore diameter distribution map of catalyst in embodiment 1.
Fig. 5 is the mesoporous distribution map of catalyst in embodiment 1.
Fig. 6 is the x-ray photoelectron spectroscopy figure of P elements in embodiment 1.
Fig. 7 is x-ray photoelectron spectroscopy (XPS) figure of cobalt element in embodiment 1.
Fig. 8 is charge/discharge capacity and the voltage curve figure of lithium-air battery in embodiment 1.
Fig. 9 is that the discharge current density of lithium-air battery in embodiment 1 is on the figure that affects of discharge capacity.
Embodiment
The invention will be further described below in conjunction with accompanying drawing, embodiment and Comparative Examples:
The characterizing method of the secondary lithium-air battery cathod catalyst of the present invention's preparation is as follows:
Adopt S-4700 SEM and TecnaiG220 TEM that the microscopic appearance of Kaolinite Preparation of Catalyst is observed; Adopt NOVA4000 gas absorption analyzer to carry out the BET specific area measuring, temperature is 77K; Employing Horvath-Kawazoe(HK) model calculates average pore size and the pore-size distribution of micropore; Adopt theoretical average pore size and the pore-size distribution that calculates mesopore of Barrett-Joyner-Halenda (BJH).Before test, sample is in 523K and 10
-3Place 10hr under the pressure of Torr, to remove adsorb oxygen and other impurity in its hole.The XPS test is completed by ESCALAB5 type energy disperse spectroscopy (VG Scientific Limited), and excitation source is Al Ka (1486.6Ev), and resolution is 0.1eV.In order to eliminate by the bad drift in conjunction with energy that causes of material conductivity, use the pollution carbon (combination of C1s can be 285.0eV) in vacuum chamber to proofread and correct.
The characterizing method of lithium-air battery of secondary lithium-air battery cathod catalyst that comprises the present invention preparation is as follows:
The present invention characterizes the performance of lithium-air battery by the electric cell tester of indigo plant.Battery testing adopts button cell, and it is the hole of 1mm that 13 diameters are arranged on the anode cover of button cell, enters the passage of battery for oxygen.The electro-chemical test step of button cell: lithium-air battery discharges and recharges in being filled with the glove box of oxygen.At first be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of emitting is with the Mass Calculation of exotic atom doping carbon material.
In following examples and Comparative Examples, the preparation method of battery is: with the n-formyl sarcolysine base pyrrolidone solution of the catalyst that obtains and 10 % Kynoar (PVDF) mixed-shaped form slurry (catalyst: Kynoar=90: 10 at normal temperatures and pressures, weight ratio), evenly be coated on nickel foam, on nickel foam, the load capacity of catalyst is 0.3mg, then 100 ℃ of vacuumizes after 5 hours, the film of gained is compressed under 10MPa pressure, the film thickness of gained is 100mm approximately, is cut into the electrode slice of f14mm as the positive pole of button cell; The negative pole of button cell uses the lithium sheet; Electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L triglyme (TEGDME) (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The preparation of embodiment 1:P and Co codope porous carbon
Take resorcinol and formaldehyde, mix, the mol ratio of resorcinol and formaldehyde is 1: 2, and adds the 50ml deionized water, and strong stirring forms uniform solution, then adds Co (NO
3)
26H
2O, the mol ratio that makes resorcinol and Co is 1: 20, and stirring and dissolving; Dropwise add again ammoniacal liquor, make solution form colloidal sol.
With above-mentioned colloidal sol at vacuum drying chamber in 85 ℃ of dryings 7 days, form gel; With this gel be placed in tube furnace under Ar atmosphere in 1000 ℃ of heat treatment 2h, obtain Co doping porous carbon.Add phosphoric acid in gained Co doping carbon, the mass ratio that makes carbon and phosphoric acid is 1: 10, and in 80 ℃ of dipping 2h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 1h at 800 ℃ in tube furnace under Ar atmosphere, naturally cool to room temperature, obtain P and Co codope porous carbon, the aperture of carbon is 0.6～120 nm, and the mol ratio of P/Co and carbon is 1: 19, and the mol ratio of P, Co is 4: 1.Catalyst to preparation characterizes, and result is as follows:
Accompanying drawing 1 is the microscopic appearance figure of above-mentioned catalyst, and exotic atom phosphorus and cobalt codope C catalyst have abundant pore structure as seen from Figure 1; Accompanying drawing 2 is the elementary analysis figure of above-mentioned catalyst, and analysis chart 2 shows that the content of phosphorus in doping carbon is 3.98 At%, and the content of cobalt is 1.04 At%, and the content of carbon is 94.98 At%.
Above-mentioned catalyst is carried out the gas absorption analytical test, and accompanying drawing 3 is N
2The adsorption desorption curve chart, as shown in Figure 3, prepared catalyst contains micropore and mesopore, and calculated specific surface area is 1153m
2/ g; Accompanying drawing 4, Fig. 5 are respectively micropore diameter distribution map and the mesoporous distribution map of above-mentioned catalyst, analyze as can be known that the pore size distribution range of the micropore of doping carbon is 6 ~ 20, and the pore size distribution range of mesopore is 20 ~ 1200.
Accompanying drawing 6, Fig. 7 are respectively the xps energy spectrum analysis chart of P elements and cobalt element in the appeal catalyst, and as seen from the figure, material with carbon element has been realized the doping of exotic atom phosphorus and cobalt.
Be prepared into button cell and test, at first be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of emitting reaches 2460 mAh/g, when discharging current increases to 1500mA/g with the Mass Calculation of exotic atom doping carbon material, the discharge capacity of this material is 1460mAh/g, the charge-discharge magnification that is equivalent to 10C, during to 6000mA/g, the discharge capacity of this battery is 1030mAh/g when further raising current density; Discharge and recharge with 30mA/g, cycle life is 420 times.Result shows that P and Co codope porous carbon have higher charge/discharge capacity, high-multiplying-power discharge performance and cyclical stability preferably preferably as cathod catalyst.
The preparation of embodiment 2:P and Fe codope porous carbon
It is that the autoclave of 100ml seals that the sucrose solution of 1M is put into volume, and compactedness is 70 v%, with autoclave in baking oven in 220 ℃ of heating 12h, obtain the intermediate of carbon; Take intermediate carbon, add the 0.1M ferric chloride solution, the mol ratio that makes Fe and intermediate carbon is 0.01: 1, after dipping 3h, in 100 ℃ of oven dry; Add again phosphoric acid, the mass ratio that makes carbon and phosphoric acid is 1: 16, in 80 ℃ of dipping 3h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 2h at 900 ℃ in tube furnace, obtain P and Fe codope porous carbon under Ar atmosphere, the aperture of carbon is 11 ~ 200 nm, the mol ratio of P/Fe and carbon is 3: 97, and the mol ratio of P, Fe is 2:1.
Be prepared into button cell and test, at first be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of emitting reaches 1600 mAh/g, when discharging current increases to 1500mA/g with the Mass Calculation of exotic atom doping carbon material, the discharge capacity of this material is 1060mAh/g, the charge-discharge magnification that is equivalent to 10C, during to 6000mA/g, the discharge capacity of this battery is 800 mAh/g when further raising current density; Discharge and recharge with 30mA/g, cycle life is 300 times.Result shows that P and Fe codope porous carbon have higher charge/discharge capacity, high-multiplying-power discharge performance and cyclical stability preferably preferably as cathod catalyst.
The preparation of embodiment 3:P, Fe and Co codope porous carbon
Take resorcinol and formaldehyde mixes, the mol ratio that makes resorcinol and formaldehyde is 1: 2, and adds 100 ml deionized waters, and strong stirring forms uniform solution, then adds Co (NO
3)
26H
2O and iron chloride, making the mol ratio of Fe, Co is 1: 1～3, is preferably 1:3, the mol ratio that makes resorcinol, Co is 1: 15, and stirring and dissolving; Dropwise add again ammoniacal liquor, make solution form colloidal sol.
With above-mentioned colloidal sol at vacuum drying chamber in 85 ℃ of dryings 10 days, form gel, with this gel be placed in tube furnace under Ar atmosphere in 1000 ℃ of heat treatment 3h, obtain Co and Fe codope porous carbon.Add phosphoric acid in gained Co and Fe codope carbon, the mass ratio that makes carbon and phosphoric acid is 1: 12, and in 80 ℃ of dipping 3h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 3h at 800 ℃ under Ar atmosphere in tube furnace, naturally cool to room temperature, obtain P and Fe, Co codope porous carbon, the aperture of carbon is 0.9～50nm.The mol ratio of P/Co/Fe and carbon is 1: 19, and the mol ratio of P, Fe is 1:1, and the mol ratio of Fe, Co is 1:3.
Be prepared into button cell and test, at first be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of emitting reaches 3200 mAh/g, when discharging current increases to 1500mA/g with the Mass Calculation of exotic atom doping carbon material, the discharge capacity of this material is 2100 mAh/g, the charge-discharge magnification that is equivalent to 10C, during to 6000mA/g, the discharge capacity of this battery is 1600mAh/g when further raising current density; Discharge and recharge with 30mA/g, cycle life is 460 times.Result shows that P and Fe, Co codope porous carbon have higher charge/discharge capacity, high-multiplying-power discharge performance and cyclical stability preferably preferably as cathod catalyst.
The preparation of embodiment 4:P and Ni codope porous carbon
The sucrose solution of 0.5M is put into autoclave seal, compactedness is 80v %, with autoclave in baking oven in 220 ℃ of heating 6h, obtain the intermediate of carbon, take intermediate carbon, add 0.1M Ni (NO
3)
26H
2O solution, the mol ratio that makes Ni and intermediate carbon is 0.005: 1, after dipping 10h, in 80 ℃ of oven dry; Add again phosphoric acid, the mass ratio that makes carbon and phosphoric acid is 1: 16, in 80 ℃ of dipping 0.5h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 1h at 900 ℃ in tube furnace, obtain P and Ni codope porous carbon under Ar atmosphere, the aperture of carbon is 4 ~ 160nm, the mol ratio of P/Ni and carbon is 3:97, and the mol ratio of P, Ni is 2:1.
The preparation of embodiment 5:P, Ni and Co codope porous carbon
Take resorcinol and formaldehyde mixes, the mol ratio that makes resorcinol and formaldehyde is 1: 2, and adds 100 ml deionized waters, and strong stirring forms uniform solution, then adds Co (NO
3)
26H
2O and Ni (NO
3)
26H
2O, the mol ratio that makes resorcinol and Co is 1: 12, the mol ratio of Co and Ni is 2: 1, and stirring and dissolving; Dropwise add again ammoniacal liquor, make solution form colloidal sol.
With above-mentioned colloidal sol at vacuum drying chamber in 85 ℃ of dryings 10 days, form gel, with this gel be placed in tube furnace under Ar atmosphere in 800 ℃ of heat treatment 5h, obtain Co and Ni codope carbon.Add phosphoric acid in gained Co and Ni codope carbon, the mass ratio that makes carbon and phosphoric acid is 1: 15, and in 80 ℃ of dipping 2h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 5h at 700 ℃ under Ar atmosphere in tube furnace, naturally cool to room temperature, obtain P and Co, Ni codope porous carbon, the aperture of carbon is 0.1 ~ 7.5nm, and the mol ratio of P/Co/Ni and carbon is 4:96, the mol ratio of P, Co is 1:1, and the mol ratio of Co, Ni is 1:2.
The preparation of embodiment 6:P and Cr codope porous carbon
The sucrose solution of 0.2M is put into autoclave seal, compactedness is 90v %, with autoclave in baking oven in 220 ℃ of heating 6h, obtain the intermediate of carbon, take intermediate carbon, add 0.2 M Cr (NO
3)
39H
2O solution, the mol ratio that makes Cr and intermediate carbon is 0.002: 1, after dipping 5h, in 80 ℃ of oven dry; Add again phosphoric acid, the mass ratio that makes carbon and phosphoric acid is 1: 12, in 80 ℃ of dipping 0.5h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 5h at 600 ℃ in tube furnace, obtain P and Cr codope porous carbon under Ar atmosphere, the aperture of carbon is 2 ~ 70 nm, the mol ratio of P/Cr and carbon is 1:99, and the mol ratio of P, Cr is 1:1.
The preparation of embodiment 7:P and Mn codope porous carbon
Take resorcinol and formaldehyde, mix, the mol ratio of resorcinol and formaldehyde is 1: 2, and adds 50 ml deionized waters, and strong stirring forms uniform solution, then adds Mn (NO
3)
2, the mol ratio that makes resorcinol and Mn is 1: 10, and stirring and dissolving; Dropwise add again ammoniacal liquor, make solution form colloidal sol.
With above-mentioned colloidal sol at vacuum drying chamber in 85 ℃ of dryings 7 days, form gel; With this gel be placed in tube furnace under Ar atmosphere in 1000 ℃ of heat treatment 3h, obtain Mn doping porous carbon.Add phosphoric acid in gained Mn doping carbon, the mass ratio that makes carbon and phosphoric acid is 1: 15, and in 80 ℃ of dipping 1h, then phosphoric acid is separated with carbon, the gained material with carbon element is heated 0.5h at 700 ℃ in tube furnace under Ar atmosphere, naturally cool to room temperature, obtain P and Mn codope porous carbon, the aperture of carbon is 0.1 ~ 2nm, and the mol ratio of P/Mn and carbon is 2:98, and the mol ratio of P and Mn is 1:1.
The preparation of Comparative Examples 1:P doping porous carbon
The material with carbon element of the P of embodiment 1-7 preparation, transition metal codope is chosen any one kind of them be dissolved in the sulfuric acid solution of 0.5M, soak a week in 85 ℃, except the transition metal in carbon elimination, with the product centrifugation that obtains, remove supernatant liquor, then lower floor solid matter with deionized water washing three times 80 ℃ of dryings 10 hours, obtains P doping porous carbon.
Take said method to remove the Co element P in embodiment 1 and Co codope porous carbon, then resulting P doping porous carbon is assembled into button cell and tests, at first be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of emitting is with the Mass Calculation of exotic atom doping carbon material, reach 1300 mAh/g, when discharging current increases to 1500mA/g, the discharge capacity of this material is 867mAh/g, the charge-discharge magnification that is equivalent to 10C, during to 6000mA/g, the discharge capacity of this battery is 650mAh/g when further raising current density; Discharge and recharge with 30mA/g, cycle life is 250 times.The performance test results of battery in comparing embodiment and Comparative Examples, show that containing phosphorus and transition metal cathod catalyst has more efficient catalytic performance than the catalyst that only contains P elements, the battery that is prepared into has higher charge/discharge capacity, better high-multiplying-power discharge performance and cyclical stability.
The preparation of embodiment 8:P and Co codope Graphene
Adopt the Hummer method to prepare graphene oxide take natural flake graphite as raw material, accurately take the 0.5g graphene oxide, the ethanolic solution that adds the 0.05M tetraphenyl phosphonium bromide, the mol ratio that makes P and graphene oxide is 0.02: 1, stirs and fully adds Co (NO after mixing
3)
26H
2O, making the mol ratio of P and Co is 4: 1, sealing in the autoclave of packing into, and compactedness is 70 %, autoclave is heated 10h in 150 ℃ in baking oven, naturally cool to room temperature, after the products therefrom freeze drying, heat 2h at 800 ℃ under Ar atmosphere in tube furnace, obtain P and Co codope Graphene, the thickness of Graphene is 3 ~ 10nm, and the mol ratio of P/Co and Graphene is 1:19, and the mol ratio of P, Co is 4:1.
Be prepared into button cell and test, at first be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of emitting reaches 4500 mAh/g, when discharging current increases to 1500mA/g with the Mass Calculation of exotic atom doping carbon material, the discharge capacity of this material is 3000mAh/g, the charge-discharge magnification that is equivalent to 10C, during to 6000mA/g, the discharge capacity of this battery is 2250mAh/g when further raising current density; Discharge and recharge with 30mA/g, cycle life is 500 times.Result shows that P and Co codope Graphene have higher charge/discharge capacity, high-multiplying-power discharge performance and cyclical stability preferably preferably as cathod catalyst.
The preparation of embodiment 9:P and Fe codope Graphene
Accurately measure ethanol 5ml in being filled with the glove box of Ar, and accurately taking tetraphenyl phosphonium bromide, the mol ratio that makes tetraphenyl phosphonium bromide and ethanol is 1:20, then adds 2 g magnesium powder, after stirring also abundant mixing, the interior sealing of the autoclave of packing into, compactedness is 70v %, and autoclave is heated 72 h in 220 ℃ in Muffle furnace, naturally cool to room temperature, the product that obtains is washed three times with deionized water, obtain the P doped graphene, the mol ratio of P/ Graphene is 2:98.Take the P doped graphene, add the 0.1M ferric chloride solution, the mol ratio that makes Fe and doped graphene is 1: 99, after dipping 10h, in 80 ℃ of oven dry, then resulting materials is heated 3h at 800 ℃ in tube furnace under Ar atmosphere, obtain P and Fe codope Graphene, the thickness of Graphene is 0.4 ~ 1nm, and the mol ratio of P/Fe and Graphene is 3:97, and the mol ratio of P, Fe is 2:1.
The preparation of embodiment 10:P and Fe codope multi-walled carbon nano-tubes
accurately measure benzene 10ml in being filled with the glove box of Ar, and accurately take triphenyl phosphorus, the mol ratio that makes triphenyl phosphorus and benzene is 1: 10, triphenyl phosphorus is dissolved in benzene, then add the 2g zinc powder, strong stirring, after fully mixing, the interior sealing of the autoclave of packing into, compactedness is 80 v %, autoclave is heated 24 h in 550 ℃ in Muffle furnace, naturally cool to room temperature, with the product centrifugation that obtains, remove supernatant liquor, lower floor's solid product washs three times with deionized water and ethanol respectively, obtain P doping multi-walled carbon nano-tubes, P, the mol ratio of multi-walled carbon nano-tubes is 1:99.Take P doping multi-walled carbon nano-tubes, add the 0.1M ferric chloride solution, the mol ratio that makes Fe and multi-walled carbon nano-tubes is 1: 99, after dipping 10h, in 80 ℃ of oven dry, then resulting materials is heated 5h at 600 ℃ in tube furnace under Ar atmosphere, obtain P and Fe codope multi-walled carbon nano-tubes, the diameter of multi-walled carbon nano-tubes is 1 ~ 100nm, and the mol ratio of P/Fe and multi-walled carbon nano-tubes is 2:98, and the mol ratio of P, Fe is 1:1.
Claims (7)
1. a secondary lithium-air battery cathod catalyst, is characterized in that, described catalyst is exotic atom doping carbon material, and wherein, exotic atom is phosphorus and transition metal; Material with carbon element is porous carbon, Graphene or multi-walled carbon nano-tubes; Wherein the mol ratio of exotic atom and carbon is 1: 19～99; The mol ratio 1～4: 1 of phosphorus and transition metal in exotic atom.
2. secondary lithium-air battery cathod catalyst according to claim 1, it is characterized in that: described transition metal is one or several in Fe, Co, Ni, Cr, Mn.
3. secondary lithium-air battery cathod catalyst according to claim 1, it is characterized in that: the aperture of described porous carbon is 0.1～200 nm.
4. secondary lithium-air battery cathod catalyst according to claim 1, it is characterized in that: the thickness of described Graphene is 0.4～10 nm.
5. secondary lithium-air battery cathod catalyst according to claim 1, it is characterized in that: the diameter of described multi-walled carbon nano-tubes is 1～100 nm.
6. secondary lithium-air battery cathod catalyst according to claim 1, it is characterized in that: the mol ratio of described exotic atom and carbon is 1: 19.
7. secondary lithium-air battery cathod catalyst according to claim 1 is characterized in that: the mol ratio 4: 1 of phosphorus and transition metal in described exotic atom.
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Cited By (7)
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| CN104282918A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Li-air battery negative electrode, Li-air battery and Li-air battery electrode preparation method |
| CN105006547A (en) * | 2014-07-30 | 2015-10-28 | 香港应用科技研究院有限公司 | Lithium-ion battery and coating method of electrode active material of lithium-ion battery |
| CN105731437A (en) * | 2016-01-26 | 2016-07-06 | 苏州大学 | Exotic-atom-doped graphene, and preparation method and application thereof |
| CN108666587A (en) * | 2017-03-29 | 2018-10-16 | 北京纳米能源与***研究所 | Anode catalyst material and its preparation method and application and metal-air battery positive electrode, metal-air battery |
| CN108892126A (en) * | 2018-07-20 | 2018-11-27 | 苏州洛特兰新材料科技有限公司 | A kind of preparation method of graphene metal composite new material |
| CN109004186A (en) * | 2018-06-15 | 2018-12-14 | 陕西科技大学 | A kind of preparation method of multiple exotic atom doping three-dimensional grapheme |
| CN115172782A (en) * | 2022-08-10 | 2022-10-11 | 山东大学 | Radial hollow rod-shaped P-Cu 2 MoS 4 And preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104282918A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Li-air battery negative electrode, Li-air battery and Li-air battery electrode preparation method |
| CN104282918B (en) * | 2013-07-02 | 2018-04-10 | 中国科学院上海硅酸盐研究所 | Lithium-air battery negative electrode, lithium-air battery and the method for preparing lithium-air battery electrode |
| CN105006547A (en) * | 2014-07-30 | 2015-10-28 | 香港应用科技研究院有限公司 | Lithium-ion battery and coating method of electrode active material of lithium-ion battery |
| CN105731437A (en) * | 2016-01-26 | 2016-07-06 | 苏州大学 | Exotic-atom-doped graphene, and preparation method and application thereof |
| CN105731437B (en) * | 2016-01-26 | 2019-01-08 | 苏州大学 | A kind of exotic atom doped graphene and the preparation method and application thereof |
| CN108666587A (en) * | 2017-03-29 | 2018-10-16 | 北京纳米能源与***研究所 | Anode catalyst material and its preparation method and application and metal-air battery positive electrode, metal-air battery |
| CN109004186A (en) * | 2018-06-15 | 2018-12-14 | 陕西科技大学 | A kind of preparation method of multiple exotic atom doping three-dimensional grapheme |
| CN108892126A (en) * | 2018-07-20 | 2018-11-27 | 苏州洛特兰新材料科技有限公司 | A kind of preparation method of graphene metal composite new material |
| CN115172782A (en) * | 2022-08-10 | 2022-10-11 | 山东大学 | Radial hollow rod-shaped P-Cu 2 MoS 4 And preparation method and application thereof |
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