CN109728297A - Metal phthalocyanine/carbon pipe composite material preparation method and its application in lithium-sulphur cell positive electrode - Google Patents
Metal phthalocyanine/carbon pipe composite material preparation method and its application in lithium-sulphur cell positive electrode Download PDFInfo
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- CN109728297A CN109728297A CN201811513176.1A CN201811513176A CN109728297A CN 109728297 A CN109728297 A CN 109728297A CN 201811513176 A CN201811513176 A CN 201811513176A CN 109728297 A CN109728297 A CN 109728297A
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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 present invention provides the application in metal phthalocyanine/carbon pipe composite material preparation method and its lithium-sulfur cell, preparation methods are as follows: by carbon pipe and sulphur simple substance mixed grinding, CS is added2It is dried after being sufficiently stirred and carbon pipe load sulphur composite material is made；It is mixed with carbon nanotube, Kynoar, metal phthalocyanine by certain mass ratio, then N-Methyl pyrrolidone is added, it stirs and ultrasonic disperse is uniform, viscosity is controlled in 1000~10000cps, obtain slurry, gained slurry is coated in current collector aluminum foil with the thickness of 150~400mm, is then dried to get metal phthalocyanine/carbon pipe composite material；Metal phthalocyanine provided by the invention/carbon pipe composite material preparation method, it is easy to operate, it is easy to be mass produced；Composite material obtained effectively inhibits shuttle effect, improves the coulombic efficiency and cyclical stability of lithium-sulfur cell for can solve dissolution of more sulphions in liquid electrolyte in lithium-sulfur cell charge and discharge process in lithium-sulfur cell.
Description
Technical field
The invention belongs to nanocomposite research field, in particular to a kind of metal phthalein for lithium-sulphur cell positive electrode
Cyanines/carbon pipe composite material preparation method and its application in lithium-sulphur cell positive electrode.
Background technique
With growing day by day, the increasingly exhausted and burning of fossil fuel reserves of rapid economic development and energy-output ratio
Caused by environmental pollution so that demand of the people to novel alternative energy source is more and more urgent.New energy, especially chemical energy source tool
Have clean and environmental protection and it is safe and efficient the features such as, meet the requirement of human kind sustainable development strategy and gain great popularity.Lithium ion battery
Since being commercialized since 1991, it is widely applied to portable electronic commnication device, power grid storage, space equipment, electronic cycling
Equal fields, show considerable commercial promise.By development in more than 20 years, the performance of the positive and negative pole material of conventional lithium ion battery
Its theoretical limit is had been approached, but still unsatisfactory in face of increasingly huger energy-storage system.
Lithium-sulfur cell theoretical specific capacity is 1675mAhg-1, theoretical specific energy is 2600WhKg-1, much higher than existing
Lithium ion battery.And the rich reserves of sulphur, cheap, low toxicity is nuisanceless.Therefore, lithium-sulfur cell becomes next-generation high specific energy
The candidate of lithium battery causes mondial concern.However, more lithium sulfides that lithium-sulfur cell is formed in charge and discharge process
It is soluble in the problems such as corrosion that volume expansion and lithium metal in shuttle effect and charge and discharge process are caused in liquid electrolyte
It causes that lithium-sulfur cell active material utilization is low, coulombic efficiency is low, poor circulation, seriously hinders its practicalization.
In order to solve these problems, its large-scale use is realized, it is necessary to research and development simplicity and lower-cost preparation
Method improves the chemical property of lithium-sulfur cell, to promote the actual application prospect of lithium-sulfur cell.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that providing a kind of system of metal phthalocyanine/carbon pipe composite material
Application in Preparation Method and its lithium-sulphur cell positive electrode.
To achieve the above object, first goal of the invention of the invention is to provide a kind of metal phthalocyanine/carbon pipe composite material
Preparation method, technical solution be the following steps are included:
(1) carbon pipe carries the preparation of sulphur composite material: carbon pipe being mixed with elemental sulfur by 1:1-2 mass ratio, after grinding uniformly
CS is added2It is stirred in feed liquid, is subsequently placed in room temperature down toward CS2After volatilization completely, surplus materials is kept the temperature in 120~160 DEG C of baking ovens
8~12h is cooled to room temperature carries sulphur composite material to get carbon pipe later；
(2) metal phthalocyanine/carbon pipe composite material preparation: carbon pipe obtained by step (1) is carried into sulphur composite material and is added with conduction
Add agent, binder to mix by 3-8:1:1 mass ratio, N-Methyl pyrrolidone and metal phthalocyanine stirring and ultrasound is then added
It is uniformly dispersed, the mass ratio that the additive amount and carbon pipe of metal phthalocyanine carry sulphur composite material is 1:20-200, controls viscosity 1000
~10000cps, obtains slurry, and gained slurry scraper is coated in current collector aluminum foil, aluminium foil is then transferred to 40~60
DEG C drying in oven is to get metal phthalocyanine/carbon pipe composite material.
Further setting is the metal phthalocyanine are as follows: FePC, Cobalt Phthalocyanine or CuPc, accordingly prepared metal
Phthalocyanine/carbon pipe composite material is respectively that FePC/carbon pipe composite material, Cobalt Phthalocyanine/carbon pipe composite material or CuPc/carbon pipe are multiple
Condensation material.Wherein, FePC/carbon pipe composite material component skeleton symbol is FePc/CNT/S, Cobalt Phthalocyanine/carbon pipe composite material group
Dividing skeleton symbol is CoPc/CNT/S, and CuPc/carbon pipe composite material component skeleton symbol is CuPc/CNT/S.
Further setting is that the current collector aluminum foil in the step (2) is using N-Methyl pyrrolidone and alcohol clear using preceding
It washes, to remove surface oxide layer and impurity, natural air drying.
It is carbon nanotube that further setting, which is the conductive additive, and the binder is Kynoar.
A second object of the present invention is to provide a kind of metal phthalocyanine as prepared by above-mentioned preparation method/carbon pipe composite wood
Material.
Third object of the present invention provides a kind of if above-mentioned metal phthalocyanine/carbon pipe composite material is in lithium-sulphur cell positive electrode
It is applied in material.
The beneficial effects of the present invention are:
(1) metal phthalocyanine/carbon pipe (FePc/CNT/S, CoPc/CNT/S or CuPc/CNT/S) anode composite material prepared
Material can be additionally provided electrons/ions pathway, reduce the internal resistance of cell, greatly enhance the discharge capacity of battery
And stable circulation performance；
(2) metal phthalocyanine/carbon pipe (FePc/CNT/S, CoPc/CNT/S or CuPc/CNT/S) composite positive pole can adsorb
Polysulfide improves lithium-sulfur cell performance to inhibit shuttle effect；
(3) carrier carbon pipe provide storage sulphur space, and can limit polysulfide, lithium sulfide diffusion and transport.
In summary, on the one hand, it is easy to operate the present invention provides metal phthalocyanine/carbon pipe composite material preparation method,
It is not related to high temperature and pressure, can be completed at room temperature, is easy to be mass produced；On the other hand, the composite material obtained is used for
In lithium-sulfur cell, dissolution of more sulphions in liquid electrolyte in lithium-sulfur cell charge and discharge process can solve, effectively inhibit
Shuttle effect improves the coulombic efficiency and cyclical stability of lithium-sulfur cell.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention.
FePC made from Fig. 1 embodiment of the present invention 1/carbon pipe composite material is for lithium-sulfur cell and is free of phthalocyanine iron material
Lithium-sulfur cell high rate performance comparison diagram；
FePC made from Fig. 2 embodiment of the present invention 1/carbon pipe composite material is for lithium-sulfur cell and is free of phthalocyanine iron material
Charge and discharge platform comparison diagram of the lithium-sulfur cell at 0.2C；
Cobalt Phthalocyanine made from Fig. 3 embodiment of the present invention 2/carbon pipe composite material is for lithium-sulfur cell and is free of Cobalt Phthalocyanine material
Lithium-sulfur cell high rate performance comparison diagram；
CuPc made from Fig. 4 embodiment of the present invention 3/carbon pipe composite material is for lithium-sulfur cell and is free of phthalocyanine copper product
Charge and discharge platform comparison diagram of the lithium-sulfur cell at 0.2C.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
It the preparation of 1 FePC of embodiment/carbon pipe composite material and is applied in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: the carbon pipe and 400mg elemental sulfur for taking 200mg are in mortar, by carbon pipe and sulphur
It is fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 4.0mL CS is added2It is sufficiently stirred, to CS2Volatilization
Completely, mixture is transferred to 120 DEG C of baking oven heat preservation 12h, be cooled to room temperature later, it is multiple up to carbon pipe load sulphur to collect products therefrom
Condensation material；
(2) FePC/carbon pipe composite material preparation: carbon pipe is carried into sulphur composite material 400mg and is received with conductive additive carbon
Then mitron 50mg, the mixing of bonding agent Kynoar 50mg, 5-10mg FePC are added 2.5mL NMP and ultrasonic disperse, fill
Divide stirring, controls the viscosity of slurry in 10000cps, be then coated in current collector aluminum foil with the thickness of 150mm scraper
(aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then
Aluminium foil is transferred in 40 DEG C of baking ovens, is dried to get required positive electrode is arrived；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, without FePC
It is stand-by that control anode pole piece is also made in carbon pipe composite material in the same way；It is being full of argon gas, water and oxygen content are respectively less than l
The assembling of battery is carried out in the glove box of ppm.Using commercial metals lithium piece as reference electrode and to electrode, using LiTFSI/
DOL.DME (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, assemble CR2025 button cell
After, it stands for 24 hours, then carries out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
Fig. 1 is FePC/carbon pipe composite material made from the present embodiment for lithium-sulfur cell and without addition FePC
The high rate performance comparison diagram of lithium-sulfur cell, from the graph, it is apparent that the lithium-sulfur cell of the positive electrode containing FePC exists
Higher discharge capacity is owned by under each multiplying power.
Fig. 2 is that FePC/carbon pipe composite material is used for lithium-sulfur cell with the lithium-sulfur cell without adding FePC in 0.2C
Under charge and discharge platform comparison diagram, FePC/carbon pipe composite material lithium-sulfur cell capacity and adopted it can be seen from the figure that having
Collection rate is substantially better than the two kinds of batteries of lithium sulphur for not adding FePC.
Embodiment 2: it the preparation of Cobalt Phthalocyanine/carbon pipe composite material and is applied in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: the carbon pipe and 400mg elemental sulfur for taking 200mg are in mortar, by carbon pipe and sulphur
It is fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 4.0mL CS is added2It is sufficiently stirred, to CS2Volatilization
Completely, mixture is transferred to 120 DEG C of baking oven heat preservation 12h, be cooled to room temperature later, it is multiple up to carbon pipe load sulphur to collect products therefrom
Condensation material；
(2) Cobalt Phthalocyanine/carbon pipe composite material preparation: carbon pipe is carried into sulphur composite material 400mg and is received with conductive additive carbon
Then mitron 50mg, the mixing of binder Kynoar 50mg, 5-10mg Cobalt Phthalocyanine are added 2.5mL NMP and ultrasonic disperse, fill
Divide stirring, controls the viscosity of slurry in 10000cps, be then coated in current collector aluminum foil with the thickness of 150mm scraper
(aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then
Aluminium foil is transferred in 40 DEG C of baking ovens, is dried to get required positive electrode is arrived；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, without Cobalt Phthalocyanine
It is stand-by that control anode pole piece is also made in carbon pipe composite material in the same way；It is being full of argon gas, water and oxygen content are respectively less than
The assembling of battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electrode, using LiTFSI/
DOL.DME (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, assemble CR2025 button cell
After, it stands for 24 hours, then carries out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
Fig. 3 is Cobalt Phthalocyanine/carbon pipe composite material made from the present embodiment for lithium-sulfur cell and without addition Cobalt Phthalocyanine
The high rate performance comparison diagram of lithium-sulfur cell, from the graph, it is apparent that the lithium-sulfur cell of the positive electrode containing Cobalt Phthalocyanine exists
Higher discharge capacity is owned by under each multiplying power.
It the preparation of 3 CuPcs of embodiment/carbon pipe composite material and is applied in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: the carbon pipe and 400mg elemental sulfur for taking 200mg are in mortar, by carbon pipe and sulphur
It is fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 4.0mL CS is added2It is sufficiently stirred, to CS2Volatilization
Completely, mixture is transferred to 120 DEG C of baking oven heat preservation 12h, be cooled to room temperature later, it is multiple up to carbon pipe load sulphur to collect products therefrom
Condensation material；
(2) CuPc/carbon pipe composite material preparation: carbon pipe is carried into sulphur composite material 400mg and is received with conductive additive carbon
Then mitron 50mg, the mixing of binder Kynoar 50mg, 5-10mg CuPc are added 2.5mL NMP and ultrasonic disperse, fill
Divide stirring, controls the viscosity of slurry in 10000cps, be then coated in current collector aluminum foil with the thickness of 150mm scraper
(aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then
Aluminium foil is transferred in 40 DEG C of baking ovens, is dried to get required positive electrode is arrived；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, without CuPc
It is stand-by that control anode pole piece is also made in carbon pipe composite material in the same way；It is being full of argon gas, water and oxygen content are respectively less than
The assembling of battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electrode, using LiTFSI/
DOL.DME (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, assemble CR2025 button cell
After, it stands for 24 hours, then carries out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
Fig. 4 is that CuPc/carbon pipe composite material is used for lithium-sulfur cell with the lithium-sulfur cell without adding CuPc in 0.2C
Under charge and discharge platform comparison diagram, it can be seen from the figure that with CuPc carbon pipe composite material lithium-sulfur cell capacity and
Acquisition rate is substantially better than the lithium-sulfur cell for not adding CuPc.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (6)
1. a kind of metal phthalocyanine/carbon pipe composite material preparation method, it is characterised in that the following steps are included:
(1) carbon pipe carries the preparation of sulphur composite material: carbon pipe being mixed with elemental sulfur by 1:1-2 mass ratio, is added after grinding uniformly
CS2It is stirred in feed liquid, is subsequently placed in room temperature down toward CS2After volatilization completely, surplus materials keeps the temperature 8 in 120~160 DEG C of baking ovens~
12h is cooled to room temperature carries sulphur composite material to get carbon pipe later；
(2) metal phthalocyanine/carbon pipe composite material preparation: by carbon pipe obtained by step (1) carry sulphur composite material and conductive additive,
Binder is mixed by 3-8:1:1 mass ratio, and N-Methyl pyrrolidone and metal phthalocyanine stirring is then added and ultrasonic disperse is equal
Even, the mass ratio that the additive amount of metal phthalocyanine and carbon pipe carry sulphur composite material is 1:20-200, control viscosity 1000~
10000cps obtains slurry, and gained slurry scraper is coated in current collector aluminum foil, aluminium foil is then transferred to 40~60 DEG C
Drying in oven is to get metal phthalocyanine/carbon pipe composite material.
2. metal phthalocyanine according to claim 1/carbon pipe composite material preparation method, it is characterised in that: the gold
Belong to phthalocyanine are as follows: FePC, Cobalt Phthalocyanine or CuPc, accordingly prepared metal phthalocyanine/carbon pipe composite material is respectively phthalocyanine
Iron/carbon pipe composite material, Cobalt Phthalocyanine/carbon pipe composite material or CuPc/carbon pipe composite material.
3. metal phthalocyanine according to claim 1/carbon pipe composite material preparation method, it is characterised in that: the step
(2) current collector aluminum foil in is using N-Methyl pyrrolidone and alcohol washes using preceding, to remove surface oxide layer and impurity, from
So air-dry.
4. metal phthalocyanine according to claim 1/carbon pipe composite material preparation method, it is characterised in that: described leads
Electric additive is carbon nanotube, and the binder is Kynoar.
5. a kind of metal phthalocyanine prepared by preparation method as described in one of claim 1-4/carbon pipe composite material.
6. a kind of metal phthalocyanine as claimed in claim 5/carbon pipe composite material is applied in lithium sulfur battery anode material.
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Cited By (3)
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| CN113066952A (en) * | 2021-03-24 | 2021-07-02 | 肇庆市华师大光电产业研究院 | Preparation method of high-catalytic-activity positive electrode material of lithium-sulfur battery |
| CN113841277A (en) * | 2019-07-18 | 2021-12-24 | 株式会社Lg新能源 | Lithium-sulfur secondary battery |
| CN113948702A (en) * | 2021-10-14 | 2022-01-18 | 温州大学 | Heme and melamine functionalized carbon nanotube biomimetic catalyst, positive electrode and battery |
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