CN107086304A - The preparation method of lithium-air battery transient metal sulfide air cathode material - Google Patents
The preparation method of lithium-air battery transient metal sulfide air cathode material Download PDFInfo
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- CN107086304A CN107086304A CN201710204134.9A CN201710204134A CN107086304A CN 107086304 A CN107086304 A CN 107086304A CN 201710204134 A CN201710204134 A CN 201710204134A CN 107086304 A CN107086304 A CN 107086304A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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 belongs to lithium air battery preparation technology field, specially a kind of preparation method of lithium-air battery transient metal sulfide air cathode material.Nickel cobalt glycerine salt, glycerine salt hydrolysis formation nickel cobalt hydroxide hollow ball, gas-phase presulfiding nickel cobalt hydroxide are prepared the invention mainly comprises hydro-thermal method.The step of the inventive method preparation technology is few, cost is low, has successfully synthesized a kind of flower-shaped NiCo with multi-stage artery structure2S4Hollow ball, effectively reduces overpotential, improves capacity and cycle life.
Description
Technical field
The invention belongs to lithium-air battery technical field, and in particular to a kind of preparation side of lithium air battery positive electrode material
Method.
Background technology
In recent decades, the battery based on lithium metal has dominated the electrochemistry of the development lithium metals of heavy-duty battery
Although capacity up to 3860 mAh/g, the electrochemistry capacitance of most of anode material for lithium-ion batteries only has 200 mAh/g left
The right side, the development of lithium ion battery greatly receives the restriction of its positive electrode.It is different from lithium ion battery, metal-air battery
Using metal as negative pole, the oxygen in air makees positive pole, as study hotspot in recent years.
Metal-air battery is made up of metal negative electrode, electrolyte and air electrode, and its air electrode can be continuously
Electrode reaction active material is drawn from surrounding environment --- oxygen, like that can only be inside cell apparatus rather than general battery
Ask for, thus metal-air battery all has very high theoretical specific energy (not including oxygen quality), 1000Wh/kg with
On, while it has nontoxic, pollution-free, discharging voltage balance, storage life length, cheap, abundant raw material, reproducible utilization
The advantages of.In this system, zinc-air battery, magnesium air cell and aluminium-air cell are by long-term widely studied, wherein zinc
Air cell has been commercialized.Lithium has minimum in minimum oxidation-reduction potential (- 3.03V vs SHE) and metallic element
Electrochemical equivalent (0.259g/Ah), so compared with other all metal-air batteries, lithium-air battery has highest
Theoretical specific energy, reaches 11400 Wh/kg, suitable with gasoline, so as to cause the strong interest of people.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lithium air battery positive electrode material-transient metal sulfide,
And the material, to improve the overpotential in the capacity of lithium-air battery, reduction charge and discharge process, is improved into its electricity as catalyst
Chemical property.
The preparation method for lithium air battery positive electrode material-transient metal sulfide that the present invention is provided, specific steps are such as
Under：
（1）Prepare nickel cobalt glycerine salt
By Ni (NO3)2·6H2O and Co (NO3)2·6H2O is added in the mixed solution of isopropanol and glycerine, and being sufficiently mixed makes its shape
Into the settled solution of aubergine；Then this solution is transferred in water heating kettle and carries out hydro-thermal reaction, hydrothermal temperature is 160
DEG C -200 DEG C, the hydro-thermal reaction time is 5-7 hour, obtains brown ceramic powder, i.e. nickel cobalt glycerine salt；
（2）Prepare nickel cobalt hydroxide
By obtained nickel cobalt glycerine salt in the liquid phase, ultrasonic agitation is well mixed to it；Then solution is transferred in water heating kettle
Hydro-thermal reaction is carried out, hydrothermal temperature is 140 DEG C -180 DEG C, and the hydro-thermal time is 7-9 hour；Room temperature is naturally cooled to, is taken
Go out suction filtration, obtain blackish green powder, i.e. nickel cobalt hydroxide；
（3）Gas-phase presulfiding prepares NiCo2S4
Above-mentioned nickel cobalt hydroxide and sulfide are taken, the two is respectively put into two porcelain boats；Porcelain boat is placed in tube furnace, lazy
Property atmosphere protection under be warming up to 300 DEG C -400 DEG C, close ventilation, calcined, the time is 3-6 hours；Naturally room temperature is down to, i.e.,
Obtain black powder, i.e. transient metal sulfide NiCo2S4。
Step of the present invention（1）In, used Ni (NO3)2·6H2O and Co (NO3)2·6H2O mol ratio is 1:1.5-
1:2.5（I.e. 1:（1.5-2.5））, preferred molar ratio is 1:2.
Step of the present invention（1）In, the volume ratio of isopropanol and glycerine is 3:1-5:1（I.e.（3-5）:1）, preferred volume ratio is
4:1。
Step of the present invention（2）In, the liquid phase is one kind in water, ethanol, methanol, isopropanol.
Step of the present invention（3）In, the sulfide is the one or more in thioacetamide, thiocarbamide.
Step of the present invention（3）In, the amount for the sulfide of vulcanization needs excessive 6-10 times.
Step of the present invention（3）In, used inert atmosphere is one kind in nitrogen, argon gas.
Advantages of the present invention：
Step of preparation process of the invention is few, cost is low, the NiCo of synthesis2S4It is Transition Metal Sulfur in the pattern of hollow bouquet
Compound brings multi-stage artery structure when being used as lithium air battery positive electrode catalyst.These multi-stage artery structures make material sheet
Body has bigger specific surface area and more reaction sites, is conducive to the transmission of oxygen and electrolyte, effectively reduces charge and discharge
The cycle life of overpotential and battery in electric process.Meanwhile, these pore passage structures also provide more spaces and put to accommodate
Electric product, effectively improves the capacity of battery.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of final product in embodiment 1.
Fig. 2 is the BET and graph of pore diameter distribution of final product in embodiment 1.
Fig. 3 is the SEM figures of final product in embodiment 1.
Fig. 4 is the TEM figures of final product in embodiment 1.
Fig. 5 is that final product is 0.1mA/cm in current density in embodiment 12When full charge and discharge test.
Fig. 6 is that final product is 0.1mA/cm in current density in embodiment 12When limited capacity loop test.
Embodiment
The present invention is hereafter further described by specific embodiment combination accompanying drawing, is not construed as limiting the invention.
Embodiment 1
（1）120ml isopropanols and 32ml glycerine are taken in beaker, stirring 5min is well mixed the two.Weigh 350mg respectively again
Ni (NO3)2·6H2O and 700mg Co (NO3)2·6H2O, adds beaker, and ultrasonic 20min continues to stir to formation aubergine
Settled solution.Then this solution is transferred in 200ml water heating kettles, is warming up to 180 DEG C of holding 6h.After naturally cool to room temperature
Afterwards, take out and 12h is dried at suction filtration, 80 DEG C, obtain brown ceramic powder；
（2）Take 300mg steps（1）In obtained powder add 60ml H2In O, ultrasonic agitation is well mixed to it.Then will be molten
Liquid is transferred in 100ml water heating kettles, is warming up to 160 DEG C, keeps 8h.After room temperature, take out and done at suction filtration, 80 DEG C
Dry 12h, obtains blackish green powder, i.e. nickel cobalt hydroxide；
（3）Weigh a certain amount of nickel cobalt hydroxide and thioacetamide（TAA）, make TAA excessive 10 times, be respectively put into the two
In two porcelain boats.Porcelain boat is placed in tube furnace, 350 DEG C is warming up to 5 DEG C/min speed under N2 protections, closes N2, keep
6h.After room temperature is down to naturally, black powder, i.e. NiCo are obtained2S4。
Shown in pattern and chemical property as Fig. 1-Fig. 5 of material manufactured in the present embodiment.
Embodiment 2
（1）120ml propyl alcohol and 32ml glycerine are taken in beaker, stirring 5min is well mixed the two.Weigh 350mg's respectively again
Ni(NO3)2·6H2O and 700mg Co (NO3)2·6H2O, adds beaker, and ultrasonic 20min continues to stir to formation aubergine
Settled solution.Then this solution is transferred in 200ml water heating kettles, is warming up to 200 DEG C of holding 5h.After naturally cool to room temperature
Afterwards, take out and 12h is dried at suction filtration, 80 DEG C, obtain brown ceramic powder；
（2）Take 200mg steps（1）In obtained powder add 60ml H2In O, ultrasonic agitation is well mixed to it.Then will be molten
Liquid is transferred in 100ml water heating kettles, is warming up to 170 DEG C, keeps 6h.After room temperature, take out and done at suction filtration, 80 DEG C
Dry 12h, obtains blackish green powder, i.e. nickel cobalt hydroxide；
（3）Weigh a certain amount of nickel cobalt hydroxide and thioacetamide（TAA）, make TAA excessive 8 times, be respectively put into the two
In two porcelain boats.Porcelain boat is placed in tube furnace, 400 DEG C is warming up to 5 DEG C/min speed under Ar protections, closes Ar gas, protect
Hold 5h.After room temperature is down to naturally, black powder, i.e. NiCo are obtained2S4。
Embodiment 3
（1）100ml isopropanols and 25ml glycerine are taken in beaker, stirring 5min is well mixed the two.Weigh 300mg respectively again
Ni (NO3)2·6H2O and 600mg Co (NO3)2·6H2O, adds beaker, and ultrasonic 20min continues to stir to formation aubergine
Settled solution.Then this solution is transferred in 200ml water heating kettles, is warming up to 170 DEG C of holding 7h.After naturally cool to room temperature
Afterwards, take out and 12h is dried at suction filtration, 80 DEG C, obtain brown ceramic powder；
（2）Take 250mg steps（1）In obtained powder add 70ml H2In O, ultrasonic agitation is well mixed to it.Then will be molten
Liquid is transferred in 100ml water heating kettles, is warming up to 150 DEG C, keeps 9h.After room temperature, take out and done at suction filtration, 80 DEG C
Dry 12h, obtains blackish green powder, i.e. nickel cobalt hydroxide；
（3）A certain amount of nickel cobalt hydroxide and thiocarbamide are weighed, makes thiocarbamide excessive 9 times, the two is put into two porcelain boats respectively.
Porcelain boat is placed in tube furnace, in N2300 DEG C are warming up to 5 DEG C/min speed under protection, 8h is kept.Treat that nature is down to room temperature
Afterwards, black powder, i.e. NiCo are obtained2S4。
The material that the pattern and chemical property of material prepared by embodiment 2 and embodiment 3 are prepared with example 1.
Claims (7)
1. a kind of preparation method of lithium-air battery transient metal sulfide air cathode material, it is characterised in that specific steps
For：
（1）Prepare nickel cobalt glycerine salt
By Ni (NO3)2·6H2O and Co (NO3)2·6H2O is added in the mixed solution of isopropanol and glycerine, and being sufficiently mixed makes its shape
Into the settled solution of aubergine；Then this solution is transferred in water heating kettle and carries out hydro-thermal reaction, hydrothermal temperature is 160
DEG C -200 DEG C, the hydro-thermal reaction time is 5-7 hour, obtains brown ceramic powder, i.e. nickel cobalt glycerine salt；
（2）Prepare nickel cobalt hydroxide
By obtained nickel cobalt glycerine salt in the liquid phase, ultrasonic agitation is well mixed to it；Then solution is transferred in water heating kettle
Hydro-thermal reaction is carried out, hydrothermal temperature is 140 DEG C -180 DEG C, and the hydro-thermal time is 7-9 hour；Room temperature is naturally cooled to, is taken
Go out suction filtration, obtain blackish green powder, i.e. nickel cobalt hydroxide；
（3）Gas-phase presulfiding prepares NiCo2S4
Above-mentioned nickel cobalt hydroxide and sulfide are taken, the two is respectively put into two porcelain boats；Porcelain boat is placed in tube furnace, lazy
Property atmosphere protection under be warming up to 300 DEG C -400 DEG C, close ventilation, calcined, the time is 3-6 hours；Naturally room temperature is down to, i.e.,
Obtain black powder, i.e. transient metal sulfide NiCo2S4。
2. preparation method according to claim 1, it is characterised in that step（1）Used in Ni (NO3)2·6H2O and
Co(NO3)2·6H2O mol ratio is 1:1.5-1:2.5.
3. preparation method according to claim 1 or 2, it is characterised in that step（1）In isopropanol and glycerine volume
Than for 3:1-5:1.
4. preparation method according to claim 3, it is characterised in that step（2）Described in liquid phase be water, ethanol, methanol,
One kind in isopropanol.
5. the preparation method according to claim 1,2 or 4, it is characterised in that step（3）Described in sulfide be thio second
One or more in acid amides, thiocarbamide.
6. preparation method according to claim 5, it is characterised in that step（3）In be used for vulcanize sulfide amount need
Excessive 6-10 times.
7. the preparation method according to claim 1,2,4 or 6, it is characterised in that step（3）Used in inert atmosphere
For one kind in nitrogen, argon gas.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108335918A (en) * | 2017-12-29 | 2018-07-27 | 中南大学 | A kind of ultracapacitor bimetallic sulfide and preparation method thereof |
| CN108609665A (en) * | 2018-05-31 | 2018-10-02 | 安阳师范学院 | Core-shell structure copolymer hollow-core construction zinc-cobalt sulfide nanosphere electrode material and preparation method thereof |
| CN108773859A (en) * | 2018-07-25 | 2018-11-09 | 安徽师范大学 | A kind of vulcanization nano material and its preparation method and application |
| CN109560294A (en) * | 2018-11-30 | 2019-04-02 | 深圳大学 | A kind of lithium oxygen battery positive electrode and preparation method thereof and lithium oxygen battery |
| CN111653800A (en) * | 2020-06-17 | 2020-09-11 | 泰州市海创新能源研究院有限公司 | Preparation method and application of self-supporting metal sulfide air electrode |
| CN112337485A (en) * | 2020-11-12 | 2021-02-09 | 中国矿业大学 | Dicobalt tetrasulfide-diindium tetrasulfide compound, preparation method and application |
| CN115611324A (en) * | 2022-11-01 | 2023-01-17 | 江苏科技大学 | Nickel-cobalt bimetal-based submicron flower cluster and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108335918A (en) * | 2017-12-29 | 2018-07-27 | 中南大学 | A kind of ultracapacitor bimetallic sulfide and preparation method thereof |
| CN108609665A (en) * | 2018-05-31 | 2018-10-02 | 安阳师范学院 | Core-shell structure copolymer hollow-core construction zinc-cobalt sulfide nanosphere electrode material and preparation method thereof |
| CN108773859A (en) * | 2018-07-25 | 2018-11-09 | 安徽师范大学 | A kind of vulcanization nano material and its preparation method and application |
| CN109560294A (en) * | 2018-11-30 | 2019-04-02 | 深圳大学 | A kind of lithium oxygen battery positive electrode and preparation method thereof and lithium oxygen battery |
| CN111653800A (en) * | 2020-06-17 | 2020-09-11 | 泰州市海创新能源研究院有限公司 | Preparation method and application of self-supporting metal sulfide air electrode |
| CN112337485A (en) * | 2020-11-12 | 2021-02-09 | 中国矿业大学 | Dicobalt tetrasulfide-diindium tetrasulfide compound, preparation method and application |
| CN115611324A (en) * | 2022-11-01 | 2023-01-17 | 江苏科技大学 | Nickel-cobalt bimetal-based submicron flower cluster and preparation method and application thereof |
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Application publication date: 20170822 |