CN103117400B - Secondary lithium-air battery cathode catalyst - Google Patents

Secondary lithium-air battery cathode catalyst Download PDF

Info

Publication number
CN103117400B
CN103117400B CN201310061860.1A CN201310061860A CN103117400B CN 103117400 B CN103117400 B CN 103117400B CN 201310061860 A CN201310061860 A CN 201310061860A CN 103117400 B CN103117400 B CN 103117400B
Authority
CN
China
Prior art keywords
carbon
catalyst
air battery
mol ratio
discharge
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310061860.1A
Other languages
Chinese (zh)
Other versions
CN103117400A (en
Inventor
杨瑞枝
吴娇
杨振荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201310061860.1A priority Critical patent/CN103117400B/en
Publication of CN103117400A publication Critical patent/CN103117400A/en
Application granted granted Critical
Publication of CN103117400B publication Critical patent/CN103117400B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

A kind of secondary lithium-air battery cathode catalyst
Technical field
The present invention relates to a kind of battery material, be specifically related to a kind of secondary lithium-air battery cathode catalyst, belong to high performance chemical electric power source eelctro-catalyst field.
Background technology
Because the fast development in the fields such as space technology, mobile communication, guided missile, Aero-Space and modern people are to the care of energy crisis, environmental protection, the research of high energy-storage battery, exploitation have caused the extensive concern of people.Because lithium is that in all metallic elements, quality is minimum, electrode potential is minimum, so the battery be made up of lithium has the features such as open circuit voltage is high, specific discharge capacity is large, instead of rapidly NI-G recent years, Ni-MH battery becomes most popular high-energy battery.
Secondary lithium-air battery is a kind of is positive electrode active materials with oxygen, take lithium metal as the battery of negative active core-shell material, also claim " lithium metal fuel cell ".Because oxygen sources is in air, inexhaustible, nexhaustible, thus secondary lithium-air battery has low, the environment amenable advantage of cost.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 conventional lithium ion battery, its performance can compare favourably with gasoline (12.22 kWh/kg).Therefore, secondary lithium-air battery has broad application prospects in the field such as portable type electronic product and communication apparatus as high-energy-density power supply of new generation, especially can meet the requirement of the high-energy-density of electric car power supply.
At present, secondary lithium-air battery is in quick development in the world.In secondary lithium-air battery charge and discharge process, air electrode (i.e. oxygen electrode) chemical property to battery as negative electrode has decisive influence.The place of metal oxide decomposition reaction is there is in air electrode when there is redox reactions and charging when being the electric discharge of secondary lithium-air battery, there is typical gas-liquid-solid phase reaction boundary zone, because the oxygen electrochemical reducting reaction of air electrode is slow and Li in course of reaction 2o 2/ Li 2the activation energy of O electrochemical oxidation precipitated oxygen is high and cause 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, catalytic center is provided for the lithium peroxide in lithium-air battery charge and discharge process forms Sum decomposition, not only affect the charge and discharge potential of secondary lithium-air battery, charge/discharge capacity 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 the cycle efficieny that battery table has revealed, charge and discharge cycles three is enclosed, and 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 synthesis macrocyclic compound is high; synthetic route is long, side reaction is many, thus improves the preparation cost (K.M.Abraham of catalyst greatly; Z.Jiang A Polymer Electrolyte ?Based Rechargeable Lithium/Oxygen Battery. J.Electrochem.Soc. 1996 143:1).
The people such as Yang have prepared noble metal nano catalyst Pt 0.5au 0.5/ C is applied in lithium-air battery, result of study shows, this catalyst has economic benefits and social benefits catalytic action, both the discharge voltage (than pure carbon height about 0.2V) of battery had been improved, again reduce the charging voltage (reducing about 0.6V than pure carbon) of battery, the remarkable efficiency for charge-discharge improving battery; Although the noble metals such as Pt, Au show excellent catalytic effect, because the price of its costliness 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. have studied the electrocatalysis characteristic of dissimilar transition metal oxide, finds that electrolytic oxidation manganese and cobalt oxide have 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); Jiaxin Li etc. adopt redox to prepare carbon and carry manganese oxide electrocatalysis material, its discharge capacity more than 1800mAh/g, discharge platform higher than 2.8V, charging platform lower than 3.8V, battery polarization significantly reduces (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, the feature of good cycle, preferably electrocatalysis characteristic, but the conductivity of transition metal oxide is bad, reaction is easily terminated, and can not give play to stable electrocatalysis characteristic.
Thus, need that research and development are more efficient, the secondary lithium-air battery cathode catalyst of low cost to promote the precipitation of oxygen in oxygen reduction and charging process in discharge process, thus the performance of raising 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 cathode catalyst, to reduce charge and discharge potential, increase charge/discharge capacity, the raising cycle efficieny of 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 cathode catalyst, and this 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; The mol ratio 1: 19 ~ 99 of exotic atom and carbon; 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 ex situ doping method.The catalyst prepared effectively can promote the generation of redox reactions when battery discharge, meanwhile, the generation that can effectively promote oxygen evolution to react again when battery charges 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 cathode catalyst, there is difunctional character, significantly can 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 catalyst agent that the present invention is made up of phosphorus, transition metal element doped material with carbon element obviously can reduce production cost, has excellent catalytic efficiency simultaneously.
Accompanying drawing explanation
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 2adsorption 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 the effect diagram of discharge current density to discharge capacity of lithium-air battery in embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, the invention will be further described:
The characterizing method of secondary lithium-air battery cathode catalyst prepared by the present invention is as follows:
S-4700 SEM and the microscopic appearance of TecnaiG220 TEM to Kaolinite Preparation of Catalyst is adopted to observe; Adopt NOVA4000 gas absorption analyzer to carry out BET specific area measuring, temperature is 77K; Adopting Horvath-Kawazoe(HK) model calculates the average pore size of micropore and pore-size distribution; Adopt average pore size and the pore-size distribution of Barrett-Joyner-Halenda (BJH) theory calculate mesopore.Before test, sample is at 523K and 10 -310hr is placed, to remove adsorb oxygen in its hole and other impurity under the pressure of Torr.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 drift of the bad combination energy caused of material conductivity, pollution carbon in a vacuum chamber (combination of C1s can be 285.0eV) is used to correct.
The characterizing method comprising the lithium-air battery of secondary lithium-air battery cathode catalyst prepared by the present invention 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, the anode cover of button cell has 13 diameters be the hole of 1mm, for oxygen enters the passage of battery.The electro-chemical test step of button cell: lithium-air battery carries out discharge and recharge in the glove box being filled with oxygen.First be discharged to 2.0V with 30mA/g, then charge to 4.2V, the capacity of releasing is with the Mass Calculation of exotic atom doping carbon material.
In following examples and comparative example, the preparation method of battery is: the nitrogen methylpyrrolidone solution of the catalyst obtained and 10 % Kynoar (PVDF) is mixed to form slurry (catalyst: Kynoar=90: 10 at normal temperatures and pressures, weight ratio), even application is in nickel foam, in nickel foam, the load capacity of catalyst is 0.3mg, then 100 DEG C of vacuumizes after 5 hours, the film of gained is tight at 10MPa pressure, the film thickness of gained is about 100mm, is cut into the positive pole of electrode slice as button cell of f14mm; The negative pole of button cell uses lithium sheet; Electrolyte is 1mol LiPF 6be dissolved in (volume ratio 1: 1) in the mixed solvent of 1L triglyme (TEGDME).By 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 50ml deionized water, and strong stirring forms uniform solution, then adds Co (NO 3) 26H 2o, makes the mol ratio of resorcinol and Co be 1: 20, and stirring and dissolving; Dropwise add ammoniacal liquor again, make solution form colloidal sol.
By above-mentioned colloidal sol at vacuum drying chamber in 85 DEG C of dryings 7 days, formed gel; This gel is placed in tube furnace under an ar atmosphere in 1000 DEG C of heat treatment 2h, obtains Co doping porous carbon.Phosphoric acid is added in gained Co doping carbon, the mass ratio of carbon and phosphoric acid is made to be 1: 10, and in 80 DEG C of dipping 2h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 1h at 800 DEG C in tube furnace under Ar atmosphere, naturally cools to room temperature, obtain P and Co codope porous carbon, the aperture of carbon is that the mol ratio of 0.6 ~ 120 nm, P/Co and carbon is 1: 19, P, the mol ratio of Co is 4: 1.Characterize the catalyst of preparation, 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%.
Carry out gas absorption analytical test to above-mentioned catalyst, accompanying drawing 3 is N 2adsorption 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, and the pore size distribution range analyzing the micropore of known 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 appeal catalyst, and as seen from the figure, material with carbon element achieves the doping of exotic atom phosphorus and cobalt.
Be prepared into button cell and test, first 2.0V is discharged to 30mA/g, then 4.2V is charged to, the capacity released, with the Mass Calculation of exotic atom doping carbon material, reaches 2460 mAh/g, when discharging current is increased to 1500mA/g, the discharge capacity of this material is 1460mAh/g, be equivalent to the charge-discharge magnification of 10C, when improving current density to 6000mA/g further, the discharge capacity of this battery is 1030mAh/g; Carry out discharge and recharge with 30mA/g, cycle life is 420 times.Result shows that P and Co codope porous carbon has higher charge/discharge capacity, preferably high-multiplying-power discharge performance and good cyclical stability as cathod catalyst.
Accompanying drawing 8 is charge/discharge capacity and the voltage curve figure of above-mentioned lithium-air battery, and curve shows that doping carbon has high reversible capacity; Accompanying drawing 9 is the effect diagram of discharge current density to discharge capacity of above-mentioned lithium-air battery, from (30mAg high current density -1~ 6000mAg -1) the high rate performance curve of exotic atom phosphorus and cobalt codope carbon is known, exotic atom phosphorus and cobalt codope carbon have excellent high-rate discharge ability.
The preparation of embodiment 2:P and Fe codope porous carbon
The sucrose solution of 1M being put into volume is that the autoclave of 100ml seals, and compactedness is 70 v%, by autoclave in an oven in 220 DEG C of heating 12h, obtains the intermediate of carbon; Take intermediate carbon, add 0.1M ferric chloride solution, make the mol ratio of Fe and intermediate carbon be 0.01: 1, after dipping 3h, in 100 DEG C of oven dry; Add phosphoric acid again, the mass ratio of carbon and phosphoric acid is made to be 1: 16, in 80 DEG C of dipping 3h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 2h at 900 DEG C in tube furnace under Ar atmosphere, and obtain P and Fe codope porous carbon, the aperture of carbon is 11 ~ 200 nm, the mol ratio of P/Fe and carbon is 3: 97, P, the mol ratio of Fe is 2:1.
Be prepared into button cell and test, first 2.0V is discharged to 30mA/g, then 4.2V is charged to, the capacity released, with the Mass Calculation of exotic atom doping carbon material, reaches 1600 mAh/g, when discharging current is increased to 1500mA/g, the discharge capacity of this material is 1060mAh/g, be equivalent to the charge-discharge magnification of 10C, when improving current density to 6000mA/g further, the discharge capacity of this battery is 800 mAh/g; Carry out discharge and recharge with 30mA/g, cycle life is 300 times.Result shows that P and Fe codope porous carbon has higher charge/discharge capacity, preferably high-multiplying-power discharge performance and good cyclical stability as cathod catalyst.
The preparation of embodiment 3:P, Fe and Co codope porous carbon
Take resorcinol and formaldehyde mixes, make the mol ratio of resorcinol and formaldehyde be 1: 2, and add 100 ml deionized waters, strong stirring forms uniform solution, then adds Co (NO 3) 26H 2o and iron chloride, make the mol ratio of Fe, Co be 1: 1 ~ 3, is preferably 1:3, makes the mol ratio of resorcinol, Co be 1: 15, and stirring and dissolving; Dropwise add ammoniacal liquor again, make solution form colloidal sol.
By above-mentioned colloidal sol at vacuum drying chamber in 85 DEG C of dryings 10 days, formed gel, this gel is placed in tube furnace under an ar atmosphere in 1000 DEG C of heat treatment 3h, obtains Co and Fe codope porous carbon.Phosphoric acid is added in gained Co and Fe codope carbon, the mass ratio of carbon and phosphoric acid is made to be 1: 12, and in 80 DEG C of dipping 3h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 3h at 800 DEG C in tube furnace under Ar atmosphere, 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, P, the mol ratio of Fe is 1:1, Fe, the mol ratio of Co is 1:3.
Be prepared into button cell and test, first 2.0V is discharged to 30mA/g, then 4.2V is charged to, the capacity released, with the Mass Calculation of exotic atom doping carbon material, reaches 3200 mAh/g, when discharging current is increased to 1500mA/g, the discharge capacity of this material is 2100 mAh/g, be equivalent to the charge-discharge magnification of 10C, when improving current density to 6000mA/g further, the discharge capacity of this battery is 1600mAh/g; Carry out 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, preferably high-multiplying-power discharge performance and good cyclical stability 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 %, by autoclave in an oven in 220 DEG C of heating 6h, obtains the intermediate of carbon, takes intermediate carbon, add 0.1M Ni (NO 3) 26H 2o solution, makes the mol ratio of Ni and intermediate carbon be 0.005: 1, after dipping 10h, in 80 DEG C of oven dry; Add phosphoric acid again, the mass ratio of carbon and phosphoric acid is made to be 1: 16, in 80 DEG C of dipping 0.5h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 1h at 900 DEG C in tube furnace under Ar atmosphere, and obtain P and Ni codope porous carbon, the aperture of carbon is 4 ~ 160nm, the mol ratio of P/Ni and carbon is 3:97, P, the mol ratio of Ni is 2:1.
The preparation of embodiment 5:P, Ni and Co codope porous carbon
Take resorcinol and formaldehyde mixes, make the mol ratio of resorcinol and formaldehyde be 1: 2, and add 100 ml deionized waters, strong stirring forms uniform solution, then adds Co (NO 3) 26H 2o and Ni (NO 3) 26H 2o, make the mol ratio of resorcinol and Co be 1: 12, Co and Ni mol ratio be 2: 1, and stirring and dissolving; Dropwise add ammoniacal liquor again, make solution form colloidal sol.
By above-mentioned colloidal sol at vacuum drying chamber in 85 DEG C of dryings 10 days, formed gel, this gel is placed in tube furnace under an ar atmosphere in 800 DEG C of heat treatment 5h, obtains Co and Ni codope carbon.Phosphoric acid is added in gained Co and Ni codope carbon, the mass ratio of carbon and phosphoric acid is made to be 1: 15, and in 80 DEG C of dipping 2h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 5h at 700 DEG C in tube furnace under Ar atmosphere, naturally cool to room temperature, obtain P and Co, Ni codope porous carbon, the aperture of carbon is the mol ratio of 0.1 ~ 7.5nm, P/Co/Ni and carbon is 4:96, the mol ratio of P, Co is 1:1, Co, the mol ratio of 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 %, by autoclave in an oven in 220 DEG C of heating 6h, obtains the intermediate of carbon, takes intermediate carbon, add 0.2 M Cr (NO 3) 39H 2o solution, makes the mol ratio of Cr and intermediate carbon be 0.002: 1, after dipping 5h, in 80 DEG C of oven dry; Add phosphoric acid again, the mass ratio of carbon and phosphoric acid is made to be 1: 12, in 80 DEG C of dipping 0.5h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 5h at 600 DEG C in tube furnace under Ar atmosphere, and obtain P and Cr codope porous carbon, the aperture of carbon is 2 ~ 70 nm, the mol ratio of P/Cr and carbon is 1:99, P, the mol ratio of 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, make the mol ratio of resorcinol and Mn be 1: 10, and stirring and dissolving; Dropwise add ammoniacal liquor again, make solution form colloidal sol.
By above-mentioned colloidal sol at vacuum drying chamber in 85 DEG C of dryings 7 days, formed gel; This gel is placed in tube furnace under an ar atmosphere in 1000 DEG C of heat treatment 3h, obtains Mn doping porous carbon.Phosphoric acid is added in gained Mn doping carbon, the mass ratio of carbon and phosphoric acid is made to be 1: 15, and in 80 DEG C of dipping 1h, then phosphoric acid is separated with carbon, gained material with carbon element is heated 0.5h at 700 DEG C in tube furnace under Ar atmosphere, naturally cools to room temperature, obtain P and Mn codope porous carbon, the mol ratio of to be the mol ratio of 0.1 ~ 2nm, P/Mn and carbon be the aperture of carbon 2:98, P and Mn is 1:1.
The preparation of comparative example 1:P doping porous carbon
The material with carbon element of the P prepared by embodiment 1-7, transition metal codope is chosen any one kind of them and is dissolved in the sulfuric acid solution of 0.5M, soak one week in 85 DEG C, except the transition metal in carbon elimination, by the product centrifugation obtained, remove supernatant liquor, lower floor's solid matter with deionized water washs three times, then 80 DEG C of dryings 10 hours, obtains P doping porous carbon.
Said method is taked by P and Co codope porous carbon in embodiment 1 to remove Co element, then the porous carbon that adulterated by obtained P is assembled into button cell and tests, first 2.0V is discharged to 30mA/g, then 4.2V is charged to, the capacity released is with the Mass Calculation of exotic atom doping carbon material, reach 1300 mAh/g, when discharging current is increased to 1500mA/g, the discharge capacity of this material is 867mAh/g, be equivalent to the charge-discharge magnification of 10C, when improving current density to 6000mA/g further, the discharge capacity of this battery is 650mAh/g; Carry out discharge and recharge with 30mA/g, cycle life is 250 times.The performance test results of battery in comparing embodiment and comparative example, show to have more efficient catalytic performance containing phosphorus and transition metal cathod catalyst than the catalyst only containing P elements, the battery be 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
Hummer method is adopted to be that graphene oxide prepared by raw material with natural flake graphite, accurately take 0.5g graphene oxide, add the ethanolic solution of 0.05M tetraphenyl phosphonium bromide, make the mol ratio of P and graphene oxide be 0.02: 1, stir and add Co (NO after abundant mixing 3) 26H 2o, make the mol ratio of P and Co be 4: 1, load sealing in autoclave, compactedness is 70 %, by autoclave in an oven in 150 DEG C of heating 10h, naturally cool to room temperature, after products therefrom freeze drying, in tube furnace, under Ar atmosphere, heat 2h at 800 DEG C, obtain P and Co codope Graphene, the thickness of Graphene is that the mol ratio of 3 ~ 10nm, P/Co and Graphene is 1:19, P, the mol ratio of Co is 4:1.
Be prepared into button cell and test, first 2.0V is discharged to 30mA/g, then 4.2V is charged to, the capacity released, with the Mass Calculation of exotic atom doping carbon material, reaches 4500 mAh/g, when discharging current is increased to 1500mA/g, the discharge capacity of this material is 3000mAh/g, be equivalent to the charge-discharge magnification of 10C, when improving current density to 6000mA/g further, the discharge capacity of this battery is 2250mAh/g; Carry out discharge and recharge with 30mA/g, cycle life is 500 times.Result shows that P and Co codope Graphene has higher charge/discharge capacity, preferably high-multiplying-power discharge performance and good cyclical stability as cathod catalyst.
The preparation of embodiment 9:P and Fe codope Graphene
Ethanol 5ml is accurately measured in the glove box being filled with Ar, and accurately take tetraphenyl phosphonium bromide, make the mol ratio of tetraphenyl phosphonium bromide and ethanol be 1:20, then add 2 g magnesium powder, stir after also fully mixing, load sealing in autoclave, compactedness is 70v %, and autoclave is heated 72 h in 220 DEG C in Muffle furnace, naturally cool to room temperature, the product obtained is spent deionized water three times, obtain P doped graphene, the mol ratio of P/ Graphene is 2:98.Take P doped graphene, add 0.1M ferric chloride solution, the mol ratio of Fe and doped graphene is made to be 1: 99, after dipping 10h, in 80 DEG C of oven dry, then resulting materials is heated 3h at 800 DEG C in tube furnace under Ar atmosphere, obtain P and Fe codope Graphene, the thickness of Graphene is that the mol ratio of 0.4 ~ 1nm, P/Fe and Graphene is 3:97, P, the mol ratio of Fe is 2:1.
The preparation of embodiment 10:P and Fe codope multi-walled carbon nano-tubes
Benzene 10ml is accurately measured in the glove box being filled with Ar, and accurately take triphenyl phosphorus, the mol ratio of triphenyl phosphorus and benzene is made to be 1: 10, triphenyl phosphorus is dissolved in benzene, then 2g zinc powder is added, strong stirring, after abundant mixing, load sealing in autoclave, compactedness is 80 v %, autoclave is heated 24 h in 550 DEG C in Muffle furnace, naturally cool to room temperature, by the product centrifugation obtained, 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 0.1M ferric chloride solution, the mol ratio of Fe and multi-walled carbon nano-tubes is made to be 1: 99, after dipping 10h, in 80 DEG C of oven dry, then resulting materials is heated 5h at 600 DEG C 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 that the mol ratio of 1 ~ 100nm, P/Fe and multi-walled carbon nano-tubes is 2:98, P, the mol ratio of Fe is 1:1.

Claims (3)

1. a secondary lithium-air battery cathode 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) of phosphorus and transition metal in exotic atom: 1; Described transition metal is one or several in Fe, Co, Ni, Cr, Mn; The aperture of described porous carbon is 0.1 ~ 200 nm; The thickness of described Graphene is 0.4 ~ 10 nm; The diameter of described multi-walled carbon nano-tubes is 1 ~ 100 nm.
2. according to the secondary lithium-air battery cathode catalyst described in claim 1, it is characterized in that: the mol ratio of described exotic atom and carbon is 1: 19.
3. according to the secondary lithium-air battery cathode catalyst described in claim 1, it is characterized in that: the mol ratio 4: 1 of phosphorus and transition metal in described exotic atom.
CN201310061860.1A 2013-02-27 2013-02-27 Secondary lithium-air battery cathode catalyst Active CN103117400B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310061860.1A CN103117400B (en) 2013-02-27 2013-02-27 Secondary lithium-air battery cathode catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310061860.1A CN103117400B (en) 2013-02-27 2013-02-27 Secondary lithium-air battery cathode catalyst

Publications (2)

Publication Number Publication Date
CN103117400A CN103117400A (en) 2013-05-22
CN103117400B true CN103117400B (en) 2015-04-22

Family

ID=48415712

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310061860.1A Active CN103117400B (en) 2013-02-27 2013-02-27 Secondary lithium-air battery cathode catalyst

Country Status (1)

Country Link
CN (1) CN103117400B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105006547B (en) * 2014-07-30 2018-03-02 香港应用科技研究院有限公司 The method for coating of lithium ion battery and its electrode active material
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102005581A (en) * 2010-10-15 2011-04-06 华南理工大学 Fuel cell cathode catalyst of P-MCNTs (Phosphor-doping Multi-Carbon Nanotubes) and preparation method thereof
CN102021677A (en) * 2010-10-13 2011-04-20 清华大学 Preparation method for carbon nanofiber containing transition metal and nitrogen element and application of carbon nanofiber in fuel-cell catalysts

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9136542B2 (en) * 2011-05-18 2015-09-15 The Ohio State University Catalysts for use in electrochemical applications and electrodes and devices using same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021677A (en) * 2010-10-13 2011-04-20 清华大学 Preparation method for carbon nanofiber containing transition metal and nitrogen element and application of carbon nanofiber in fuel-cell catalysts
CN102005581A (en) * 2010-10-15 2011-04-06 华南理工大学 Fuel cell cathode catalyst of P-MCNTs (Phosphor-doping Multi-Carbon Nanotubes) and preparation method thereof

Also Published As

Publication number Publication date
CN103117400A (en) 2013-05-22

Similar Documents

Publication Publication Date Title
CN108923030B (en) Preparation method of sulfur/cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium-sulfur battery positive electrode material
CN109037704B (en) Nitrogen-doped 3D porous carbon material and preparation method and application thereof
CN103413689B (en) Prepare graphene aerogel and the method for graphene/metal oxide aeroge
Zeng et al. Enhanced Li-O2 battery performance, using graphene-like nori-derived carbon as the cathode and adding LiI in the electrolyte as a promoter
CN103117400B (en) Secondary lithium-air battery cathode catalyst
You et al. Multifunctional MoSe2@ rGO coating on the cathode versus the separator as an efficient polysulfide barrier for high-performance lithium-sulfur battery
CN102593556B (en) Lithium air or oxygen battery
CN106129374B (en) A kind of transition metal oxide/binary carbon net anode composite material and aluminium ion battery
CN104157860B (en) sodium-selenium cell and preparation method thereof
CN104009205A (en) Hollow graphene ball and preparation method and application thereof
CN103811731A (en) Graphene-sulfur composite electrode material, preparation method and application thereof
CN105826523A (en) Lithium-sulfur battery positive pole material and preparation method thereof
CN102820456B (en) Porous carbon/sulfur composite material, its preparation method and application
CN108428870B (en) Large-scale preparation method and application of two-dimensional carbon sheet aerogel material compounded by metal and metal derivatives thereof
Deng et al. Synergies of the crystallinity and conductive agents on the electrochemical properties of the hollow Fe3O4 spheres
CN103560019B (en) A kind of zinc ion hybrid super capacitor
CN106505246A (en) A kind of preparation method of multistage loose structure mangano-manganic oxide/carbon nanosheet lithium ion battery negative material
CN111013631A (en) Novel three-dimensional grading porous composite material, preparation method and application thereof
CN106410194A (en) Composite lithium battery and preparation method thereof
CN103825030B (en) A kind of three-dimensional grapheme based combined electrode and its preparation method and application
CN103346333B (en) A kind of secondary lithium-air battery cathode catalyst and application thereof
Zhang et al. α-MnO 2 hollow clews for rechargeable Li-air batteries with improved cyclability
Dong et al. Atomically dispersed Co-N4C2 catalytic sites for wide-temperature Na-Se batteries
CN103825003A (en) Three-dimensional porous Co3O4/Pt/Ni combined electrode, its preparation method and its application
Li et al. Designing Electrochemical Nanoreactors to Accelerate Li2S1/2 Three-Dimensional Growth Process and Generating More Li2S for Advanced Li–S Batteries

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant