CN106450191A - Positive electrode material of lithium-sulfur battery - Google Patents
Positive electrode material of lithium-sulfur battery Download PDFInfo
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- CN106450191A CN106450191A CN201610889957.5A CN201610889957A CN106450191A CN 106450191 A CN106450191 A CN 106450191A CN 201610889957 A CN201610889957 A CN 201610889957A CN 106450191 A CN106450191 A CN 106450191A
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- lithium
- porous carbon
- sulfur battery
- positive electrode
- electrode material
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/625—Carbon or graphite
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 relates to a positive electrode material of a lithium-sulfur battery, and belongs to the technical field of a lithium-sulfur battery material. The positive electrode material of the lithium-sulfur battery is characterized by comprising the following components in a compounding manner based on mass percentage: 14-16% of honeycomb-shaped porous carbon nanofibers, 7-9% of carbon nanotubes, 54-56% of sulfur, 10-14% of super P and 9-11% of polyvinylidene fluoride. The preparation method for the positive electrode material comprises the steps of 1) preparing the honeycomb-shaped porous carbon nanofibers; 2) performing acidizing on the porous carbon fibers and the carbon nanotubes; 3) performing high-temperature heat treatment on the porous carbon nanofibers/carbon nanotubes/sulfur complex; and 4) forming the positive electrode material of the lithium-sulfur battery. The lithium-sulfur battery assembled by the positive electrode material has the characteristics of high initial charge-discharge specific capacity, stable battery cycling performance and other excellent properties, so that the positive electrode material has wide application prospect in the lithium-sulfur battery.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, belong to battery material technical field.
Background technology
Lithium-sulfur cell is existed in nature in a large number due to selected sulphur, nontoxic and low cost, and lithium metal is to gather around in nature
There are minimum standard current potential (- 3.04Vvs.SHE), minimum density (0.53g cm-3) and chemical equivalent (0.26g A-1·h-1) with
And highest theoretical specific capacity (3861mAh g-1), add that this battery has high theoretical specific capacity (1675mAh g-1) and
Energy density (2600Wh kg-1) so as to become one of first-selection of heavy-duty battery research.Although lithium-sulfur cell has in theory
At a relatively high energy density, but due to its battery, " shuttle effect " in charge and discharge process leads to battery capacity to decline rapidly
Subtract, fettered lithium-sulfur cell and promoted in actual utilization.So-called " shuttle effect " refers in battery discharge procedure by sulphur simple substance
The long-chain polysulphides of reduction, from anode, are perforated through battery diaphragm, reach GND.In the process due to many
Sulfide is dissolved in electrolyte, and it occurs a series of corresponding reactions so that positive and negative between the positive pole and negative pole of lithium-sulfur cell
Pole active material loses and brings the serious self discharge of battery.In this process, the reaction occurring will be consumed the sulphur compound of activity
With the lithium on negative pole, and it generates Li on negative pole2S2And Li2S covers on the top layer of negative pole lithium, causes the serious pole of cathode of lithium
Change.Secondly, the electronic conductivity (5 × 10 of elemental sulfur-30S/cm) and ionic conductivity is all very low, lead to the electricity of positive electrode
Chemism and utilization rate are also relatively low therewith.Additionally, positive electrode great Volume Changes in charge and discharge process also make lithium
The specific discharge capacity of sulphur battery declines rapidly.
For the problems referred to above, there is the fiber of property and porous carbon materials also attract people to note.Because hollow is fine
Dimension is suitable for anode volume change and provides good conductive path, Li et al. (Li et al., J.Power Sources,
2012,212,179-185) and Zhang et al. (Zhang et al., J.Power Sources, 2015,274,338-
344) positive electrode will be applied to, but its complex technical process, and hinder the shuttle effect of polysulfide limited, porous carbon materials by
Also it is widely used in lithium sulfur battery anode material in high specific surface area and good electric conductivity, but general material with carbon element holds
Easily reunite and its electronics conduction pathway is obstructed.
Content of the invention
The problem existing for above-mentioned background technology, it is an object of the invention to combine the excellent of carbon fiber and porous material
Point is it is proposed that a kind of porous carbon nanofiber/CNT/sulphur is combined lithium sulfur battery anode material.This cellular porous
Structure be conducive to high conductive channel, and the porous carbon fiber of its rock-steady structure can greatly suppress the shuttle of polysulfide
Effect.Meanwhile, the CNT of application overlength high conductivity works in coordination with the short or long-range electron building different levels and ion channel.
And the porous carbon fiber being acidified and carbon nano tube surface give more hydroxyl, this is conducive to being formed and polysulfide between
Strong combination is such that it is able to effectively suppress the shuttle effect of polysulfide.This kind of method can improve filling of lithium-sulfur cell
Specific discharge capacity, energy density and heat endurance and cycle life.
The present invention provide a kind of lithium sulfur battery anode material it is characterised in that：
Its by cellular porous carbon nano-fiber, CNT, sulphur, super P and five kinds of material compositions of Kynoar,
Described cellular porous carbon nano-fiber, CNT, the mass percent prescription of sulphur, super P and Kynoar are：
In lithium sulfur battery anode material, the cellular porous carbon fiber structure of acidifying is conducive to provide enough storage sulphur skies
Between and easily conductive channel, and contain because cellular porous carbon fiber has surface after rock-steady structure and acidified process
Substantial amounts of hydroxyl, this can greatly suppress the shuttle effect of polysulfide, and in addition this cellular porous carbon fiber has to environment
The feature that close friend, process is simple, production efficiency height and industrial production are easily implemented.
In lithium sulfur battery anode material, CNT can apply the high conductivity characteristic of its overlength to build difference to work in coordination with
The short or long-range electron of level and ion channel, are so greatly improved the conductance of lithium-sulphur cell positive electrode.
Described porous carbon nanofiber/CNT/sulphur be combined lithium sulfur battery anode material it is characterised in that：Described
Cellular porous carbon fiber and CNT need to be positioned over 60 DEG C the nitric acid of 1M in acidification 8～12h.Acidification
Purpose mainly removes the impurity in cellular porous carbon fiber, and it is substantial amounts of that cellular porous carbon fiber surface is had
Hydroxyl, the hydroxyl on these surfaces during lithium-sulfur cell charge and discharge cycles, can with polysulfide formed chemical bond, so its
The shuttle effect of polysulfide can greatly be suppressed.
Described lithium sulfur battery anode material is it is characterised in that its preparation method comprises the steps：1) cellular many
Hole carbon nano-fiber preparation；2) porous carbon fiber and CNT acidifying are processed；3) porous carbon nanofiber/CNT/sulphur
Complex high-temperature heat treatment；4) lithium sulfur battery anode material shaping.Lithium sulfur battery anode material preparation process of the present invention is simple, side
Just, preparation method is environmentally friendly, suitable industrialized production.The invention provides a kind of porous carbon nanofiber/CNT/
Sulphur is combined lithium sulfur battery anode material, it is an object of the invention to combining the advantage of doughnut and porous carbon materials, provides one
Plant porous carbon nanofiber/CNT/sulphur and be combined lithium-sulphur cell positive electrode material preparation method.Due to using above technical side
Case, the lithium-sulfur cell of the present invention has the characteristics that：
In compound lithium sulfur battery anode material, the cellular porous carbon fiber structure of acidifying is conducive to provide and easily leads
Electric channel, and can greatly suppress the shuttle effect of polysulfide in the porous carbon fiber due to rock-steady structure, and porous knot
Structure is adapted to the big Volume Changes in cyclic process of battery；
CNT in compound lithium sulfur battery anode material can apply the high conductivity characteristic of its overlength to work in coordination with structure
Build the short of different levels or long-range electron and ion channel.
3) porous carbon fiber being acidified and carbon nano tube surface give more hydroxyl, this be conducive to polysulfide it
Between form strong combination such that it is able to effectively suppress polysulfide shuttle effect.
Above-mentioned 3 features make prepared to lithium-sulfur cell there is more excellent chemical property, it is main that include should
The method of kind can improve charging and discharging capacity, energy density and heat endurance and the cycle life of lithium-sulfur cell.The present invention provides
Lithium sulfur battery anode material preparation method, is the exploitation of high-performance lithium-sulfur cell provides a new way.
Brief description
Fig. 1 is to be combined the lithium-sulfur cell of lithium sulfur battery anode material in difference with porous carbon nanofiber/CNT/sulphur
Charge-discharge performance under multiplying power and coulombic efficiency result figure.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
(1) present invention is first according to the patent of invention of this seminar application：A kind of lithium sulfur battery anode material porous
Carbon nanofiber membrane and preparation method thereof (CN105161722A), based on this, prepares cellular porous carbon nanofiber,
(2) the business CNT of the porous carbon fiber in above-mentioned steps (1) and purchase is positioned over the nitre of 60 DEG C of 1M
Acidified process in acid.
(3), after above-mentioned steps being mixed according to the sulphur of 70: 25: 5 ratios, porous carbon fiber and CNT, put
Put in 155 DEG C in vacuum drying chamber, heated at constant temperature 24 hours, obtain described lithium sulfur battery anode material.
(4) the invention provides a kind of porous carbon nanofiber/CNT/sulphur is combined lithium sulfur battery anode material preparation
Method, the battery of its assembling includes：There is high potential positive-active anode pole piece (mainly by sulphur/porous carbon fiber/CNT
Composite, superP and polytetrafluoroethylene (PTFE) composition, its ratio is 8: 1: 1)；There is electronegative potential negative pole lithium material；And interval
Celgard 2400 barrier film between cathode pole piece and anode pole piece, described lithium-sulfur cell carries out charge and discharge under the multiplying power of 0.5C
Electricity, its discharge cycles is as shown in Figure 1.
Embodiment 2
(1) present invention is first according to the patent of invention of this seminar application：A kind of lithium sulfur battery anode material porous
Carbon nanofiber membrane and preparation method thereof (CN105161722A) prepares cellular porous carbon nanofiber,
(2) the business CNT of the porous carbon fiber in above-mentioned steps (1) and purchase is positioned over the nitre of 60 DEG C of 1M
Acidified process in acid.
(3), after above-mentioned steps being mixed according to the sulphur of 70: 25: 5 ratios, porous carbon fiber and CNT, put
Put in 155 DEG C in vacuum drying chamber, heated at constant temperature 24 hours, obtain described lithium sulfur battery anode material.
(4) the invention provides a kind of porous carbon nanofiber/CNT/sulphur is combined lithium sulfur battery anode material preparation
Method, the battery of its assembling includes：There is high potential positive-active anode pole piece (mainly by sulphur/porous carbon fiber/CNT
Composite, superP and polytetrafluoroethylene (PTFE) composition, its ratio is 8: 1: 1)；There is electronegative potential negative pole lithium material；And interval
Celgard 2400 barrier film between cathode pole piece and anode pole piece, described lithium-sulfur cell carries out discharge and recharge under the multiplying power of 1C,
Its discharge cycles is as shown in Figure 1.
Embodiment 3
(1) present invention is first according to the patent of invention of this seminar application：A kind of lithium sulfur battery anode material porous
Carbon nanofiber membrane and preparation method thereof (CN105161722A) prepares cellular porous carbon nanofiber,
(2) the business CNT of the porous carbon fiber in above-mentioned steps (1) and purchase is positioned over the nitre of 60 DEG C of 1M
Acidified process in acid.
(3), after above-mentioned steps being mixed according to the sulphur of 70: 25: 5 ratios, porous carbon fiber and CNT, put
Put in 155 DEG C in vacuum drying chamber, heated at constant temperature 24 hours, obtain described lithium sulfur battery anode material.
(4) the invention provides a kind of porous carbon nanofiber/CNT/sulphur is combined lithium sulfur battery anode material preparation
Method, the battery of its assembling includes：There is high potential positive-active anode pole piece (mainly by sulphur/porous carbon fiber/CNT
Composite, superP and polytetrafluoroethylene (PTFE) composition, its ratio is 8: 1: 1)；There is electronegative potential negative pole lithium material；And interval
Celgard 2400 barrier film between cathode pole piece and anode pole piece, described lithium-sulfur cell carries out discharge and recharge under the multiplying power of 2C,
Its discharge cycles is as shown in Figure 1.
The foregoing is only the preferred embodiments of the present invention, not thereby limit the scope of the claims using the present invention.
Claims (2)
1. a kind of lithium sulfur battery anode material it is characterised in that：Its by cellular porous carbon nano-fiber, CNT, sulphur,
Super P and five kinds of material compositions of Kynoar, described cellular porous carbon nano-fiber, CNT, sulphur, super P
Mass percent prescription with Kynoar is：
2. porous carbon nanofiber/CNT/sulphur as claimed in claim 1 is combined lithium sulfur battery anode material, its feature
It is：Acidification 8～12h in the nitric acid of 1M that described cellular porous carbon fiber and CNT need to be positioned over 60 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610889957.5A CN106450191A (en) | 2016-10-11 | 2016-10-11 | Positive electrode material of lithium-sulfur battery |
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| CN201610889957.5A CN106450191A (en) | 2016-10-11 | 2016-10-11 | Positive electrode material of lithium-sulfur battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910943A (en) * | 2017-03-31 | 2017-06-30 | 东莞市永邦新能源科技有限公司 | A kind of high-rate lithium battery manufacturing process |
| WO2019158891A1 (en) | 2018-02-19 | 2019-08-22 | Arkema France | Active material formulation for li-s battery and preparation process |
| CN111554888A (en) * | 2020-04-09 | 2020-08-18 | 天津工业大学 | Anode material containing rabbit hair hollow carbon fibers for lithium-sulfur battery and preparation method thereof |
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| CN104766943A (en) * | 2015-03-27 | 2015-07-08 | 中国科学院金属研究所 | Preparation method and application of high-energy density lithium sulfur battery electrode |
| CN105161722A (en) * | 2015-10-16 | 2015-12-16 | 天津工业大学 | Porous carbon nanofiber membrane for positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN105489901A (en) * | 2015-12-31 | 2016-04-13 | 河南师范大学 | Preparation method and application of lithium-sulfur battery three-dimensional carbon current collector |
| CN105529464A (en) * | 2016-01-22 | 2016-04-27 | 南京航空航天大学 | Lithium-sulfur battery |
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- 2016-10-11 CN CN201610889957.5A patent/CN106450191A/en active Pending
Patent Citations (5)
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| CN102832379A (en) * | 2012-09-29 | 2012-12-19 | 上海空间电源研究所 | Preparation method of positive material for lithium-sulfur battery |
| CN104766943A (en) * | 2015-03-27 | 2015-07-08 | 中国科学院金属研究所 | Preparation method and application of high-energy density lithium sulfur battery electrode |
| CN105161722A (en) * | 2015-10-16 | 2015-12-16 | 天津工业大学 | Porous carbon nanofiber membrane for positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN105489901A (en) * | 2015-12-31 | 2016-04-13 | 河南师范大学 | Preparation method and application of lithium-sulfur battery three-dimensional carbon current collector |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910943A (en) * | 2017-03-31 | 2017-06-30 | 东莞市永邦新能源科技有限公司 | A kind of high-rate lithium battery manufacturing process |
| CN106910943B (en) * | 2017-03-31 | 2019-11-15 | 广东永邦新能源股份有限公司 | A kind of high-rate lithium battery manufacturing process |
| WO2019158891A1 (en) | 2018-02-19 | 2019-08-22 | Arkema France | Active material formulation for li-s battery and preparation process |
| FR3078201A1 (en) * | 2018-02-19 | 2019-08-23 | Arkema France | ACTIVE MATERIAL FORMULATION FOR LI-S ACCUMULATOR AND PROCESS FOR PREPARING THE SAME |
| CN111758175A (en) * | 2018-02-19 | 2020-10-09 | 阿科玛法国公司 | Active material formulation for lithium-sulfur battery and preparation method |
| JP2021514104A (en) * | 2018-02-19 | 2021-06-03 | アルケマ フランス | Active material formulation and preparation method for LI-S batteries |
| CN111554888A (en) * | 2020-04-09 | 2020-08-18 | 天津工业大学 | Anode material containing rabbit hair hollow carbon fibers for lithium-sulfur battery and preparation method thereof |
| CN111554888B (en) * | 2020-04-09 | 2022-04-29 | 天津工业大学 | Anode material containing rabbit hair hollow carbon fibers for lithium-sulfur battery and preparation method thereof |
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Application publication date: 20170222 |