CN105047950B - A kind of positive pole of lithium-air battery and preparation method thereof and lithium-air battery - Google Patents
A kind of positive pole of lithium-air battery and preparation method thereof and lithium-air battery Download PDFInfo
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- CN105047950B CN105047950B CN201510344558.6A CN201510344558A CN105047950B CN 105047950 B CN105047950 B CN 105047950B CN 201510344558 A CN201510344558 A CN 201510344558A CN 105047950 B CN105047950 B CN 105047950B
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention discloses a kind of positive pole of lithium-air battery and preparation method thereof lithium-air battery, the method that the present invention is modified using high-temperature process, to TiO2Carry out high-temperature process and obtain the TiO with a large amount of Lacking oxygens2‑x, then by TiO2‑xMain painting membrane substance is mixed into the NCNTs after acidifying, the lithium air battery positive electrode piece containing modifying titanium dioxide catalyst is obtained.Lithium air battery positive electrode piece containing modifying titanium dioxide catalyst greatly improves the stability and cyclicity of lithium-air battery, and under current density higher, the cycle-index of battery has exceeded 400 times.
Description
Technical field
The present invention relates to electrochemical energy source domain, more particularly to a kind of positive pole of lithium-air battery and preparation method thereof and lithium
Air cell.
Background technology
Lithium-air battery has high energy density, and theoretically more than the 10 of lithium ion battery times, such as lithium air is electric
Pond can be successfully applied to electric automobile, then be expected to realize and the comparable course continuation mileage of fuel-engined vehicle (500 kilometers of ＞), and this will be right
The long range of Electric Cars in China is galloped and electrical power storage field produces revolutionary impact.Lithium-air battery is by air
Lithium ion and electron reaction generation lithium peroxide (Li in oxygen molecule and battery2O2) to produce electric energy, therefore its another significant advantage
It is that the active material oxygen of positive pole is directed to surrounding air, and inside battery need not be stored in, so both reduces
Cost alleviates the weight of battery again.
At present, lithium-air battery still has many key issues urgently to be resolved hurrily in it is commercialized road：The generation of Li dendrite,
Aqueous vapor and carbon dioxide are to the activation polarization in terms of the pollution of battery, the unstability of electrolyte and air electrode in air
Deng.Wherein, the activation polarization on air electrode, current effective solution is the reference of catalyst.Catalyst adds
Plus can significantly alleviate the activation polarization of lithium-air battery, to extend the service life of battery.A large amount of experts and scholars both at home and abroad
Research extensively and profoundly is carried out to lithium-air battery catalyst, effect of the catalyst in lithium-air battery essentially consists in following
Three aspects：(1) stabilization intermediate product and discharging product；(2) electrode reaction invertibity and specific discharge capacity are improved；(3) change
Response path, improves energy conversion efficiency.And in the last few years, the research direction of air electrode catalyst is concentrated mainly on new material
With two aspects of composite.Conventional air electrode catalyst material can be divided into following 4 type：(a) carbon material；B () is expensive
Metal and alloy；(c) metal oxide materials；(d) soluble catalyst.Exactly in the numerous studies of air electrode catalyst
Under, just promote lithium-air battery to be able to great-leap-forward development, catalyst is in the research of lithium-air battery in occupation of very important
Status.
Various catalyst used have respective advantage and defect, such as noble metal catalyst in lithium-air battery, though
So it has the most prominent catalytic performance, but itself is relatively costly, and density is big, be unfavorable for it is practical with it is commercialized
Development.Soluble catalyst shows fabulous catalytic effect in the case where low current is close, but if it applies close in electric current higher
Under degree, perhaps can be not sufficiently stable, because the catalyst dissolution is in the middle of electrolyte, not only will be from electrolyte in different current densities
Under the conditions of there is preferably compatibility, but also O is resisted in charge and discharge process2 -Attack, this is in specific application
Extremely difficult realization.The strengths and weaknesses of several main flow catalyst of Comprehensive Correlation, metal oxide catalyst is excellent with what is protruded very much
Gesture, because metallic catalyst is not only cheap and easy to get, stability and high efficiency, and plasticity is high, can construct various suitable lithiums empty
The structure type that pneumoelectric pond uses, such as 3D be netted, cellular and vertical three-dimensional shape.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide the positive pole and its system of a kind of lithium-air battery
Preparation Method and lithium-air battery, the positive pole of lithium-air battery enter using modifying titanium dioxide as catalyst by titanium dioxide
Row is modified, makes it have the ability of strong adsorption of oxygen, can effectively alleviate in the prior art lithium-air battery in high current
Exist under density because oxygen supplies activation polarization phenomenon that is not enough and causing, to lift the cycle life of lithium-air battery.
Technical scheme is as follows：
A kind of preparation method of the positive pole of lithium-air battery, wherein, comprise the following steps：
A, under the protection of argon gas to TiO2Carry out high-temperature process to be modified, obtain modified TiO2-x；
B, acidification is carried out to NCNTs；
C, by modified TiO2-xMixed grinding is carried out in proportion with the NCNTs after acidifying, obtains film slurry；
D, film slurry is coated on collector, dried, obtain the positive pole of lithium-air battery；
Wherein, after acidifying NCNTs and modified TiO2-xBetween mass ratio be 9：0~4：5.
The preparation method of the positive pole of described lithium-air battery, wherein, step b specifically includes following steps：
It is by volume 0.5~1 by concentrated nitric acid and the concentrated sulfuric acid：1~3 is mixed, and prepares nitration mixture；
NCNTs is poured into nitration mixture, ultrasound 8~12 hours of backflow, temperature control is at 30 DEG C~50 DEG C.
The preparation method of the positive pole of described lithium-air battery, wherein, step a specifically includes following steps：
TiO is sintered under argon gas protection2, sintering temperature is warming up to 450~600 DEG C in 1h, is incubated 0.5~2.5h, then
900~1200 DEG C are warming up in 1h, 1~3h is incubated, modified TiO is obtained2-x。
The preparation method of the positive pole of described lithium-air battery, wherein, step c specifically includes following steps：
PVDF is dissolved in NMP；
By modified TiO2-xIt is ground in dry environment with the NCNTs after acidifying and is well mixed, is placed in dissolved with PVDF's
In nmp solution, magnetic agitation blending.
The preparation method of the positive pole of described lithium-air battery, wherein, the consumption of PVDF for film stock quality 5%~
10%.
The preparation method of the positive pole of described lithium-air battery, wherein, in step d, drying temperature is 50-80 DEG C.
The preparation method of the positive pole of described lithium-air battery, wherein, in step d, the collector is carbon paper.
The preparation method of the positive pole of described lithium-air battery, wherein, NCNTs and modified TiO after acidifying2-xBetween
Mass ratio is 8：1~6：3.
A kind of positive pole of lithium-air battery, wherein, using the preparation method system of the positive pole of lithium-air battery as described above
It is standby to obtain.
A kind of lithium-air battery, wherein, the positive pole comprising lithium-air battery as described above.
Beneficial effect：The method that the present invention is modified using high-temperature process, to TiO2High-temperature process is carried out to obtain with a large amount of
The TiO of Lacking oxygen2-x, then by TiO2-xMain painting membrane substance is mixed into the NCNTs after acidifying, wherein NCNTs is used as catalysis
Agent carrier and positive conductive agent, TiO2-xAs anode catalyst.With TiO2-xIt is lithium-air battery catalyst, in electric current higher
Under density, more oxygen can be adsorbed and enter inside battery, there is provided enough electrochemical reaction raw materials, electric discharge is alleviated significantly
During produce activation polarization, so as to improve the cycle performance of battery, make the lithium-air battery performance of preparation significantly excellent
In general lithium-air battery, even better than some lithium-air batteries with noble metal as catalyst.And, TiO2-xPreparation
Process is simple is convenient, and raw material sources are cheap and easy to get.In addition, the catalyst carrier that the present invention is used is NCNTs, with preferable
Nitrogen is doped with the ability of supported catalyst, and the CNT, to discharging product Li2O2Formation and decomposition all have
Certain positive role.Therefore the combination for passing through these two aspects so that the combination property of lithium-air battery is greatly reinforced.
Brief description of the drawings
Fig. 1 is the SEM figures of the positive plate without catalyst in the embodiment of the present invention 1.
Fig. 2 be the embodiment of the present invention 4 in contain 30%TiO2-xThe SEM figures of the positive plate of catalyst.
Fig. 3 is voltage-specific volume spirogram in the lithium-air battery charge and discharge process without catalyst in the embodiment of the present invention 1.
Fig. 4 is voltage-circulation figure in the lithium-air battery charge and discharge process without catalyst that embodiment 1 is obtained.
Fig. 5 be the embodiment of the present invention 4 in contain 30%TiO2-xVoltage in the lithium-air battery charge and discharge process of catalyst-
Specific volume spirogram.
Fig. 6 be embodiment 4 obtain contain 30%TiO2-xVoltage in the lithium-air battery charge and discharge process of catalyst-follow
Ring figure.
Specific embodiment
The present invention provides a kind of positive pole of lithium-air battery and preparation method thereof lithium-air battery, to make mesh of the invention
, technical scheme and effect it is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that described herein
Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
A kind of preparation method of the positive pole of the lithium-air battery provided in the present invention, comprises the following steps：
The first step, to TiO under the protection of argon gas2High-temperature process is carried out to be modified：
By TiO2It is placed in tube furnace, is sintered under conditions of argon gas protection gas, sintering temperature is to be heated up in 1h
To 450~600 DEG C, 0.5~2.5h is incubated, then is warming up to 900~1200 DEG C in 1h, be incubated 1~3h, obtain modified TiO2-x。
Use high-temperature process TiO2, the TiO with Lacking oxygen can be obtained2-x(scope of X is 0.01~0.1), the ability of its adsorption of oxygen
There is lifting with electric conductivity.
Second step, the CNT (NCNTs) to N doping is pre-processed：
It is by volume 0.5~1 by concentrated nitric acid and the concentrated sulfuric acid：1~3 is mixed, and prepares nitration mixture；NCNTs is poured into mixed
In acid, it is placed in there-necked flask, ultrasound 8~12 hours of backflow, temperature control obtains dispersiveness more preferably at 30 DEG C~50 DEG C
NCNTs.With the NCNTs after acid treatment as positive pole collective supported catalyst, the conductive energy of NCNTs is good, and N element
There are the deposition beneficial to product lithium peroxide and decomposition.
3rd step, by modified TiO2-xMixed grinding is carried out in proportion with the NCNTs after being processed through nitration mixture：
PVDF is dissolved in 1-METHYLPYRROLIDONE (NMP)；By modified TiO2-xExist with the NCNTs after being processed through nitration mixture
It is ground in dry environment, when so that TiO2-xUniformly mix with NCNTs, and during in having glossiness grey powder, will grind
Mixture afterwards is placed in the nmp solution dissolved with PVDF, is blended in magnetic stirring apparatus, forms mixing film slurry.Its
In, NCNTs and TiO2-xBetween mass ratio can be 9：0~4：5, the content of general catalyst is typically led not over 50%
The content of electric agent is more than 50%.Preferably, CNTs and TiO2-xBetween mass ratio can be 8：1~6：3, using this ratio model
Enclose, effect is preferable.The effect of PVDF is binding agent, by active material, i.e. NCNTs and TTiO2-xIt is bonded on collector carbon paper,
The positive pole that can be used so can be just prepared, its consumption can be the 5%~10% of mixing film stock quality.N- methyl pyrroles
Used as dispersant, depending on the addition of dispersant is according to actual conditions, general addition is about the 3 of active material total amount to pyrrolidone
~5 times, can also further be added according to actual conditions in subsequent step.
4th step, film：
First collector is placed on the evacuated panel of automatic film applicator, mixing film slurry is coated in the one of collector
End, under the promotion of automatic film applicator, uniform coating is carried out with the speed of 10-15mm per second, obtains slurry dispersed just
Pole piece；Put it into baking oven, under the conditions of 50-80 DEG C, dry 1-METHYLPYRROLIDONE, obtain with the TiO that is modified2-xIt is catalysis
The lithium air cathode piece of agent.Finally, the anode pole piece that can be used can be cut into according to the model of lithium-air battery.Lithium air
The cutting of battery pole piece is completed with manual sheet-punching machine, when positive plate carries out punching, by positive plate with after clean paper doubling
Encase carries out punching again, is polluted on positive plate with being infected with during the punching for preventing the impurity on sheet-punching machine.Positive plate
Should be preserved in the case where room temperature environment is dried.
After such scheme, the method that the present invention is modified using high-temperature process, to TiO2High-temperature process is carried out to be had
There is the TiO of a large amount of Lacking oxygens2-x, then by TiO2-xMain painting membrane substance is mixed into the NCNTs after acidifying, wherein NCNTs makees
It is catalyst carrier and positive conductive agent, TiO2-xAs anode catalyst.With TiO2-xIt is lithium-air battery catalyst, higher
Current density under, more oxygen can be adsorbed and enter inside battery, there is provided enough electrochemical reaction raw materials, alleviate significantly
The activation polarization produced in discharge process, so as to improve the cycle performance of battery, makes the lithium-air battery performance of preparation
It is significantly better than general lithium-air battery, even better than some lithium-air batteries with noble metal as catalyst.
A kind of positive pole of the lithium-air battery prepared using above-mentioned preparation method also provided in the present invention, including
Collector and the active material layer being coated on collector；The active material layer includes the CNT of N doping
(NCNTs), be modified TiO2-xCatalyst, Kynoar (PVDF).Wherein, NCNTs and TiO2-xBetween mass ratio can be
9：0~4：5.In the active material, with TiO2-xIncrease, the color of the positive pole is also by black gradually canescence.PVDF's
Consumption can be the 5%~10% of mixing film stock quality.The collector can be carbon paper, and carbon paper is in loose structure, and
The excellent electric conductivity of tool.The raw material usage of pole piece is variable, according to certain proportioning raw material usage can be from milligram level to
Kilogram level, the electrode area correspondence made is multiplied.
A kind of lithium-air battery is also provided in the present invention, the lithium-air battery is including above-mentioned lithium-air battery just
Pole.The lithium-air battery open-circuit voltage scope is 2.95V~3.12V.With TiO2-xThe lithium-air battery of catalyst is in stabilization
Property, all achieve substantial breakthrough in cyclicity, greatly improve the stability and cyclicity of lithium-air battery, keeping filling
Specific discharge capacity is 1000mAh/g, voltage range under conditions of 2.0~5.0V, setting current density is 0.3mA/cm2Under,
The cycle performance of battery has exceeded 400 times, if by process modification, being expected to break through 600 circulations.
TiO2-xMore oxygen, to make up at higher current densities, oxygen in battery can be adsorbed by way of chemisorbed
The problem that gas supply is not enough, so as to substantially reduce activation polarization of the battery in discharge process, and TiO2-xPreparation technology letter
It is single convenient, and raw material sources are cheap and easy to get.The TiO for preparing2-xStable in catalytic performance is efficiently, electric in the lithium air for using at present
Advantage in the catalyst of pond is particularly pertinent.In addition, the catalyst carrier that the present invention is used is NCNTs, urged with preferably load
Nitrogen is doped with the ability of agent, and the CNT, to discharging product Li2O2Formation and decompose all have it is certain
Positive role.Therefore the combination for passing through these two aspects so that the combination property of lithium-air battery is greatly reinforced.The present invention is empty in lithium
A brand-new trial in gas field of batteries, even more one of anode catalyst of best results, the ring for using in addition so far
Fourth sulfone electrolyte system is to prove that an ion-transfer environment for stabilization can be provided in lithium-air battery, therefore lithium of the invention is empty
The breakthrough for all being achieved in stability, cyclicity and practicality to a certain extent in pneumoelectric pond.
Below by way of specific embodiment, the present invention will be further described.
Embodiment 1
The pretreating process of NCNTs is：Take 10g NCNTs, with agate mortar hand lapping 1h, then by NCNTs pour into by
Concentrated nitric acid and the concentrated sulfuric acid are by volume 1：In the middle of 1 nitration mixture being made, it is placed in there-necked flask, ultrasound 10 hours of backflow, temperature
Degree control afterwards, is washed with deionized water to neutrality at 30 DEG C~50 DEG C, obtains dispersiveness more preferably NCNTs.
The preparation technology of positive pole is：First, 1g PVDF are dissolved in NMP, next takes the NCNTs 9g after nitration mixture treatment
0.5~1h is ground in dry environment, the mixture after grinding is placed in the nmp solution dissolved with PVDF, stirred in magnetic force
3~6h of stirring in device is mixed, rotating speed is 1000r/min, eventually forms the mixing film slurry with certain viscosity.Slurry will be smeared
The one end on the carbon paper for being placed in evacuated panel is gently poured on one side, while the container of mobile dress film slurry, is heated using high wind
And under the promotion of automatic spray dryer, uniform coating is carried out with the speed of 10-15mm per second.This process is obtained with glossy
, the positive plate of moistening, finally, put it into and dried NMP with 60-80 DEG C of temperature in drying box, using manual sheet-punching machine pair
Positive plate is cut, and obtains the lithium air battery positive electrode piece without catalyst.
What is obtained in the present embodiment is free from the positive plate of catalyst, and its SEM image is as shown in Figure 1.By gained positive plate
For preparing lithium-air battery, using metal lithium sheet as negative pole, 1M LiTFSI/ sulfolane is electrolyte, prepares lithium air electricity
Pond, and its specific capacity and cycle performance in charge and discharge process is tested, testing result is as shown in Figure 3 and Figure 4.Using without urging
The lithium-air battery that the positive plate of agent is prepared, is 2.0 for 1000mAh/g, voltage range charging and discharging capacity is kept
Under conditions of~5.0V, setting current density is 0.3mA/cm2Under, its cycle performance is only 165 circles.
Embodiment 2
TiO2-xPreparation technology be：Take the TiO of 100 nanometers of 10g2It is placed in tube furnace, in argon gas (99.99%) protection
It is sintered under conditions of gas, sintering temperature is that 600 DEG C are warming up in 1h, is incubated 1h, then 1000 DEG C, guarantor are warming up in 1h
Warm 2h, after terminating, makes to naturally cool to room temperature under conditions of product is consistent with sintering atmosphere in the tube furnace, after sintering
Immediately with vacuum sealing is carried out after sample taking-up, it is placed in and same time is placed in drier, obtains the TiO with Lacking oxygen2-x。
The pretreating process of NCNTs is：10g NCNTs agate mortar hand lapping 1h are taken, then NCNTs is poured into by dense
Nitric acid and the concentrated sulfuric acid are by volume 1：In the middle of 1 nitration mixture for preparing, it is placed in there-necked flask, ultrasound 10 hours of backflow, temperature
Control afterwards, is washed with deionized water to neutrality at 30 DEG C~50 DEG C, obtains dispersiveness more preferably NCNTs.
The preparation technology of positive pole is：First, 1g PVDF are dissolved in NMP, next takes TiO2-xAfter 1g is processed with nitration mixture
NCNTs 8g 0.5~1h is ground in dry environment, when being ground to TiO2-xMix with NCNTs to material in light
During the uniform grey sprills in pool, the mixture after grinding is placed in the nmp solution dissolved with PVDF, is stirred in magnetic stirring apparatus
3~6h is mixed, rotating speed is 1000r/min, eventually form the mixing film slurry with certain viscosity.Slurry one side will be smeared gently
The one end on the carbon paper for being placed in evacuated panel is poured into, while the container of mobile dress film slurry, is heated and automatic using high wind
Under the promotion of film dryer, uniform coating is carried out with the speed of 10-15mm per second.This process is obtained with glossiness, moistening
Positive plate, finally, put it into and dried NMP with 60-80 DEG C of temperature in drying box, positive plate is entered using manual sheet-punching machine
Row cuts, and obtains containing 10%TiO2-xThe lithium air battery positive electrode piece of catalyst.
Obtain being containing 10%TiO in the present embodiment2-xThe positive plate of catalyst, the battery assembled using the positive plate it is flat
Equal open-circuit voltage is 3.0V, battery in the case where keeping specific capacity to be 1000mAh/g, can normally run more than 400 times and follow
Ring.
Embodiment 3
TiO2-xPreparation technology be：Take the TiO of 100 nanometers of 10g2It is placed in tube furnace, in argon gas (99.99%) protection
It is sintered under conditions of gas, sintering temperature is that 600 DEG C are warming up in 1h, is incubated 1h, then 1000 DEG C, guarantor are warming up in 1h
Warm 2h, after terminating, makes to naturally cool to room temperature under conditions of product is consistent with sintering atmosphere in the tube furnace, after sintering
Immediately with vacuum sealing is carried out after sample taking-up, it is placed in and same time is placed in drier, obtains the TiO with Lacking oxygen2-x。
The pretreating process of NCNTs is：10g NCNTs agate mortar hand lapping 1h are taken, then NCNTs is poured into by dense
Nitric acid and the concentrated sulfuric acid are by volume 1：In the middle of 1 nitration mixture for preparing, it is placed in there-necked flask, ultrasound 10 hours of backflow, temperature
Control afterwards, is washed with deionized water to neutrality at 30 DEG C~50 DEG C, obtains dispersiveness more preferably NCNTs.
The preparation technology of positive pole is：First, 1g PVDF are dissolved in NMP, next takes TiO2-xAfter 2g is processed with nitration mixture
NCNTs 7g 0.5~1h is ground in dry environment, when being ground to TiO2-xMix with NCNTs to material in light
During the uniform grey sprills in pool, the mixture after grinding is placed in the nmp solution dissolved with PVDF, is stirred in magnetic stirring apparatus
3~6h is mixed, rotating speed is 1000r/min, eventually form the mixing film slurry with certain viscosity.Slurry one side will be smeared gently
The one end on the carbon paper for being placed in evacuated panel is poured into, while the container of mobile dress film slurry, is heated and automatic using high wind
Under the promotion of film dryer, uniform coating is carried out with the speed of 10-15mm per second.This process is obtained with glossiness, moistening
Positive plate, finally, put it into and dried NMP with 60-80 DEG C of temperature in drying box, positive plate is entered using manual sheet-punching machine
Row cuts, and obtains containing 20%TiO2-xThe lithium air battery positive electrode piece of catalyst.
Obtain being containing 20%TiO in the present embodiment2-xThe positive plate of catalyst, the battery assembled using the positive plate it is flat
Equal open-circuit voltage is 3.0V, battery in the case where keeping specific capacity to be 1000mAh/g, can normally run more than 400 times and follow
Ring.
Embodiment 4
TiO2-xPreparation technology be：Take the TiO of 100 nanometers of 10g2It is placed in tube furnace, in argon gas (99.99%) protection
It is sintered under conditions of gas, sintering temperature is that 600 DEG C are warming up in 1h, is incubated 1h, then 1000 DEG C, guarantor are warming up in 1h
Warm 2h, after terminating, makes to naturally cool to room temperature under conditions of product is consistent with sintering atmosphere in the tube furnace, after sintering
Immediately with vacuum sealing is carried out after sample taking-up, it is placed in and same time is placed in drier, obtains the TiO with Lacking oxygen2-x。
The pretreating process of NCNTs is：10g NCNTs agate mortar hand lapping 1h are taken, then NCNTs is poured into by dense
Nitric acid and the concentrated sulfuric acid are by volume 1：In the middle of 1 nitration mixture for preparing, it is placed in there-necked flask, ultrasound 10 hours of backflow, temperature
Control afterwards, is washed with deionized water to neutrality at 30 DEG C~50 DEG C, obtains dispersiveness more preferably NCNTs.
The preparation technology of positive pole is：First, 1g PVDF are dissolved in NMP, next takes TiO2-xAfter 3g is processed with nitration mixture
NCNTs 6g 0.5~1h is ground in dry environment, when being ground to TiO2-xMix with NCNTs to material in light
During the uniform grey sprills in pool, the mixture after grinding is placed in the nmp solution dissolved with PVDF, is stirred in magnetic stirring apparatus
3~6h is mixed, rotating speed is 1000r/min, eventually form the mixing film slurry with certain viscosity.Slurry one side will be smeared gently
The one end on the carbon paper for being placed in evacuated panel is poured into, while the container of mobile dress film slurry, is heated and automatic using high wind
Under the promotion of film dryer, uniform coating is carried out with the speed of 10-15mm per second.This process is obtained with glossiness, moistening
Positive plate, finally, put it into and dried NMP with 60-80 DEG C of temperature in drying box, positive plate is entered using manual sheet-punching machine
Row cuts, and obtains containing 30%TiO2-xThe lithium air battery positive electrode piece of catalyst.
What is obtained in the present embodiment is containing 30%TiO2-xThe positive plate of catalyst, its SEM image is as shown in Figure 2.By gained
Positive plate is used to prepare lithium-air battery, and using metal lithium sheet as negative pole, 1M LiTFSI/ sulfolane is electrolyte, prepares lithium empty
Pneumoelectric pond, and its specific capacity and cycle performance in charge and discharge process is tested, testing result is as shown in Figure 5 and Figure 6.Keeping
Charging and discharging capacity is 1000mAh/g, voltage range under conditions of 2.0~5.0V, setting current density is 0.3mA/cm2
Under, the cycle performance of battery has exceeded 400 times.
Embodiment 5
TiO2-xPreparation technology be：Take the TiO of 100 nanometers of 10g2It is placed in tube furnace, in argon gas (99.99%) protection
It is sintered under conditions of gas, sintering temperature is that 600 DEG C are warming up in 1h, is incubated 1h, then 1000 DEG C, guarantor are warming up in 1h
Warm 2h, after terminating, makes to naturally cool to room temperature under conditions of product is consistent with sintering atmosphere in the tube furnace, after sintering
Immediately with vacuum sealing is carried out after sample taking-up, it is placed in and same time is placed in drier, obtains the TiO with Lacking oxygen2-x。
The pretreating process of NCNTs is：10g NCNTs agate mortar hand lapping 1h are taken, then NCNTs is poured into by dense
Nitric acid and the concentrated sulfuric acid are by volume 1：In the middle of 1 nitration mixture for preparing, it is placed in there-necked flask, ultrasound 10 hours of backflow, temperature
Control afterwards, is washed with deionized water to neutrality at 30 DEG C~50 DEG C, obtains dispersiveness more preferably NCNTs.
The preparation technology of positive pole is：First, 1g PVDF are dissolved in NMP, next takes TiO2-xAfter 4g is processed with nitration mixture
NCNTs 5g 0.5~1h is ground in dry environment, when being ground to TiO2-xMix with NCNTs to material in light
During the uniform grey sprills in pool, the mixture after grinding is placed in the nmp solution dissolved with PVDF, is stirred in magnetic stirring apparatus
3~6h is mixed, rotating speed is 1000r/min, eventually form the mixing film slurry with certain viscosity.Slurry one side will be smeared gently
The one end on the carbon paper for being placed in evacuated panel is poured into, while the container of mobile dress film slurry, is heated and automatic using high wind
Under the promotion of film dryer, uniform coating is carried out with the speed of 10-15mm per second.This process is obtained with glossiness, moistening
Positive plate, finally, put it into and dried NMP with 60-80 DEG C of temperature in drying box, positive plate is entered using manual sheet-punching machine
Row cuts, and obtains containing 40%TiO2-xThe lithium air battery positive electrode piece of catalyst.
Obtain being containing 40%TiO in the present embodiment2-xThe positive plate of catalyst, the battery assembled using the positive plate it is flat
Equal open-circuit voltage is 3.0V, battery in the case where keeping specific capacity to be 1000mAh/g, can normally run more than 400 times and follow
Ring.
Embodiment 6
TiO2-xPreparation technology be：Take the TiO of 100 nanometers of 10g2It is placed in tube furnace, in argon gas (99.99%) protection
It is sintered under conditions of gas, sintering temperature is that 600 DEG C are warming up in 1h, is incubated 1h, then 1000 DEG C, guarantor are warming up in 1h
Warm 2h, after terminating, makes to naturally cool to room temperature under conditions of product is consistent with sintering atmosphere in the tube furnace, after sintering
Immediately with vacuum sealing is carried out after sample taking-up, it is placed in and same time is placed in drier, obtains the TiO with Lacking oxygen2-x。
The pretreating process of NCNTs is：10g NCNTs agate mortar hand lapping 1h are taken, then NCNTs is poured into by dense
Nitric acid and the concentrated sulfuric acid are by volume 1：In the middle of 1 nitration mixture for preparing, it is placed in there-necked flask, ultrasound 10 hours of backflow, temperature
Control afterwards, is washed with deionized water to neutrality at 30 DEG C~50 DEG C, obtains dispersiveness more preferably NCNTs.
The preparation technology of positive pole is：First, 1g PVDF are dissolved in NMP, next takes TiO2-xAfter 5g is processed with nitration mixture
NCNTs 4g 0.5~1h is ground in dry environment, when be ground to TiO2-x mix with NCNTs to material in have light
During the uniform grey sprills in pool, the mixture after grinding is placed in the nmp solution dissolved with PVDF, is stirred in magnetic stirring apparatus
3~6h is mixed, rotating speed is 1000r/min, eventually form the mixing film slurry with certain viscosity.Slurry one side will be smeared gently
The one end on the carbon paper for being placed in evacuated panel is poured into, while the container of mobile dress film slurry, is heated and automatic using high wind
Under the promotion of film dryer, uniform coating is carried out with the speed of 10-15mm per second.This process is obtained with glossiness, moistening
Positive plate, finally, put it into and dried NMP with 60-80 DEG C of temperature in drying box, positive plate is entered using manual sheet-punching machine
Row cuts, and obtains containing 50%TiO2-xThe lithium air battery positive electrode piece of catalyst.
Obtain being containing 50%TiO in the present embodiment2-xThe positive plate of catalyst, the battery assembled using the positive plate it is flat
Equal open-circuit voltage is 3.0V, battery in the case where keeping specific capacity to be 1000mAh/g, can normally run more than 400 times and follow
Ring.
It should be appreciated that application of the invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or converted, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Shield scope.
Claims (10)
1. a kind of preparation method of the positive pole of lithium-air battery, it is characterised in that comprise the following steps：
A, under the protection of argon gas to TiO2Carry out high-temperature process to be modified, obtain modified TiO2-x, wherein the scope of x be 0.01~
0.1；
B, acidification is carried out to NCNTs；
C, by modified TiO2-xMixed grinding is carried out in proportion with the NCNTs after acidifying, obtains film slurry；
D, film slurry is coated on collector, dried, obtain the positive pole of lithium-air battery；
Wherein, after acidifying NCNTs and modified TiO2-xBetween mass ratio be 8：1~4：5.
2. the preparation method of the positive pole of lithium-air battery according to claim 1, it is characterised in that step b is specifically included
Following steps：
It is by volume 0.5~1 by concentrated nitric acid and the concentrated sulfuric acid：1~3 is mixed, and prepares nitration mixture；
NCNTs is poured into nitration mixture, ultrasound 8~12 hours of backflow, temperature control is at 30 DEG C~50 DEG C.
3. the preparation method of the positive pole of lithium-air battery according to claim 2, it is characterised in that step a is specifically included
Following steps：
TiO is sintered under argon gas protection2, sintering temperature is warming up to 450~600 DEG C in 1h, is incubated 0.5~2.5h, then in 1h
900~1200 DEG C are warming up to, 1~3h is incubated, modified TiO is obtained2-x。
4. the preparation method of the positive pole of the lithium-air battery according to Claims 2 or 3, it is characterised in that step c is specifically wrapped
Include following steps：
PVDF is dissolved in NMP；
By modified TiO2-xIt is ground in dry environment with the NCNTs after acidifying and is well mixed, is placed in the NMP dissolved with PVDF
In solution, magnetic agitation blending.
5. the preparation method of the positive pole of lithium-air battery according to claim 4, it is characterised in that the consumption of PVDF is to apply
The 5%~10% of film stock quality.
6. the preparation method of the positive pole of lithium-air battery according to claim 5, it is characterised in that in step d, drying temperature
Spend is 50-80 DEG C.
7. the preparation method of the positive pole of lithium-air battery according to claim 6, it is characterised in that in step d, the collection
Fluid is carbon paper.
8. the preparation method of the positive pole of lithium-air battery according to claim 1, it is characterised in that the NCNTs after acidifying
With modified TiO2-xBetween mass ratio be 8：1~6：3.
9. a kind of positive pole of lithium-air battery, it is characterised in that electric using the lithium air as described in any one of claim 1~8
The preparation method of the positive pole in pond is prepared.
10. a kind of lithium-air battery, it is characterised in that the positive pole comprising lithium-air battery as claimed in claim 9.
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