CN204156016U - A kind of anode pole piece and secondary cell - Google Patents
A kind of anode pole piece and secondary cell Download PDFInfo
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- CN204156016U CN204156016U CN201420669451.XU CN201420669451U CN204156016U CN 204156016 U CN204156016 U CN 204156016U CN 201420669451 U CN201420669451 U CN 201420669451U CN 204156016 U CN204156016 U CN 204156016U
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- pole piece
- anode pole
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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
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Abstract
The utility model discloses a kind of anode pole piece is applied in secondary aluminium cell, and described anode pole piece comprises conductive substrates, positive electrode material layer and micro-porous adsorption layer.Wherein, positive electrode material layer is made up of the conductive array grown in conductive substrates and the active matter material sulphur be attached on array, has three-dimensional conductive network configuration; Micro-porous adsorption layer is positioned at above positive electrode material layer, and have the strong adsorptivity of high-ratio surface sum and bound, the interpolation of micro-porous adsorption layer can adsorb polysulfide further, improves cycle performance and the high rate performance of battery.
Description
Technical field
the utility model relates to a kind of anode pole piece and adopts the secondary cell of this anode pole piece.
Background technology
along with the fast development of the new powers such as electronics and communication apparatus, electric automobile, wind power generation and photovoltaic generation, the battery performance demand of the mankind to supporting power supply is more and more higher, have that energy is high, cost is low, the life-span is long in the urgent need to exploitation, environmental protection, the electrokinetic cell of battery material aboundresources and reusable edible and energy-storage battery.The theoretical energy density of aluminium, up to 2980mAh/g, is only second to lithium (3682mAh/g), and volume and capacity ratio is 8050mAh/cm
3
, be 4 times of lithium, and chemical activity being relatively stable, is desirable negative material; Sulphur has the theoretical energy density of 1675mAh/g, is the positive electrode that known energy density is the highest.Therefore, the two can form a kind of aboundresources as positive and negative pole material, pollution-free, cheap, energy density is high, the ideal battery of use safety.
although elemental sulfur has the lot of advantages such as specific capacity is high, cost is low as positive electrode, there is the problems such as the fast and cycle life of poor electric conductivity, capacity attenuation is short, and exist because many lithium sulfides dissolve " the flying shuttle phenomenon " caused in the electrolytic solution.In order to overcome the defect that elemental sulfur exists, normally elemental sulfur is loaded in the material with carbon element with high-specific surface area, high porosity and excellent conductive performance, form composite positive pole, dissolve in electrolyte to limit sulfur-based compound in cyclic process, but this method short-term can only suppress the stripping of sulphur.
in order to better suppress polysulfide dissolving, the utility model applies a layer superfine fibre micro-porous adsorption layer on anode pole piece, micro-porous adsorption layer has narrow micropore size, high specific area, relative to meso-hole structure, to polysulfide, there is higher constraint effect, so micro-porous adsorption layer more effectively can be adsorbed on the polysulfide produced in charge and discharge process, polysulfide is stoped to move to negative pole with electrolyte, suppress the generation of " flying shuttle phenomenon ", thus improve the performance and used life of battery.
Summary of the invention
(1) goal of the invention
the utility model provides a kind of anode pole piece with three-dimensional conductive network configuration and micro-porous adsorption layer, effectively can adsorb polysulfide, improves the performance and used life of battery.
conductive array is ordered arrangement, and there is pore structure, the three-dimensional network conducting matrix grain of the nano-scale formed, the advantages such as specific surface is huge, absorption affinity is strong, good stability, electro transfer and charge transfer are fast, the network configuration of its nano-scale has strong absorption confinement effect, with sulphur compound tense, more active material load byte can be provided, sulphur is connected with conducting matrix grain on nanoscale, greatly promote activity and the utilance of sulphur, but also can fetter and suppress the dissolving of the intermediate products such as polysulfide, thus slow down the loss of sulphur.But the hole on conductive array or the gap between array belong to meso-hole structure, to the constraint limited use of polysulfide, battery is after discharge and recharge for several times, there is the stripping of sulphur, the utility model is at conducting three-dimensional structure positive electrode top layer coating microcellular structure superfine fibre adsorption layer, it has high conductivity, high specific area and very narrow aperture, relative meso-hole structure, micropore has stronger adsorbent constraint effect to polysulfide can play further constraint effect to the polysulfide departing from three-dimensional structure constraint, the utilance of further raising active material.
the utility model also discloses a kind of secondary aluminium cell using described anode pole piece, effectively can improve high rate performance and the cyclical stability of battery.
(2) technical scheme
the above-mentioned object of the utility model is achieved by following scheme:
a kind of anode pole piece, comprise conductive substrates and positive electrode material layer, it is characterized in that, described anode pole piece also comprises the micro-porous adsorption layer be coated on positive electrode material layer.
anode pole piece described in scheme, is characterized in that, described conductive substrates is the metals or nonmetal such as carbon paper, carbon fiber, nickel, aluminium, iron, copper, zinc, lead, manganese, conductive plastics, conductive rubber or highly doped silicon.
anode pole piece described in scheme, is characterized in that, described positive electrode material layer is made up of conductive array and the active material sulphur be attached on array, have three-dimensional conductive network configuration, and vertical-growth is in conductive substrates.
anode pole piece described in scheme, is characterized in that, described conductive array is any one in carbon nano pipe array, graphene array or carbon fiber array.
anode pole piece described in scheme, is characterized in that, described micro-porous adsorption layer is made up of sorbing material and binding agent, and thickness is 5 ~ 8 μm.
anode pole piece described in scheme, is characterized in that, described sorbing material is superfine nano activated carbon fiber, and fibre diameter is Nano grade, and specific area is 1000 ~ 1300m
2
/ g, Micropore volume is 0.4 ~ 0.45cm
3
/ g, micro-pore diameter is 0.54 ~ 0.66nm.
scheme secondary aluminium cell, comprise battery container and be positioned at battery core assembly and the electrolyte of battery container inside, battery core assembly comprises the anode pole piece, barrier film and the cathode pole piece that stack gradually, it is characterized in that, described anode pole piece is anode pole piece according to claim 1, cathode pole piece is the active material containing aluminium, and electrolyte is that non-water is containing aluminium electrolyte.
the preparation method of secondary aluminium cell described in scheme (electrochemical appliance) is as follows: anode pole piece is lived be cut into 40mm wide × the long pole piece of 15mm, the barrier film thick with 0.16mm and be wound into battery core with aluminium flake as the negative pole that negative active core-shell material is made and load nickel plating box hat, reinject electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
the anode pole piece of what the utility model provided have three-dimensional conductive network configuration and micro-porous adsorption layer has following beneficial effect:
(1) the conductive array ordered arrangement of vertical-growth in conductive substrates, there is pore structure, the three-dimensional network conducting matrix grain of the nano-scale formed, specific surface is huge, absorption affinity is strong, good stability, the network configuration of electro transfer and its nano-scale of advantage such as charge transfer is fast has strong absorption confinement effect, with sulphur compound tense, more active material load byte can be provided, sulphur is connected with conducting matrix grain on nanoscale, greatly promote activity and the utilance of sulphur, but also can fetter and suppress the dissolving of the intermediate products such as polysulfide, thus slow down the loss of sulphur.
(2) there is microcellular structure superfine nano activated fibre adsorption layer, it has high conductivity, high specific area and very narrow aperture, relative meso-hole structure, micropore has stronger adsorbent constraint effect to polysulfide can play further constraint effect to the polysulfide departing from three-dimensional structure constraint, improves the utilance of active material further.
(3) secondary aluminium cell comprising this positive pole has good high rate performance and cycle performance.
(4) accompanying drawing explanation
fig. 1 is the anode pole piece structural representation of tradition without adsorption layer.
fig. 2 is the anode pole piece structural representation of band adsorption layer described in the utility model.
fig. 3 is the structural representation of secondary aluminium cell described in the utility model.
wherein a-conductive substrates, b-positive electrode material layer, c-micro-porous adsorption layer, 1-positive plate, 2-negative plate, 3-barrier film, 4-positive collector, 5-anode ear, 6-negative collector, 7-negative electrode lug.
(5) embodiment
be described further below with reference to the technique effect of embodiment to design of the present utility model, concrete structure and generation, to understand the purpose of this utility model, characteristic sum effect fully.The following examples describe several execution mode of the present utility model, and they are only illustrative, and nonrestrictive.
as shown in Figure 1, described in this embodiment, tradition comprises conductive substrates a, positive electrode material layer b without the anode pole piece of adsorption layer, and wherein positive electrode material layer is made up of the conductive array of vertical-growth in conductive substrates and the active material sulphur be attached on array.
as shown in Figure 2, anode pole piece described in this embodiment comprises conductive substrates a, positive electrode material layer b and be coated in micro-porous adsorption layer c, wherein positive electrode material layer b is made up of the conductive array of vertical-growth in conductive substrates and the active material sulphur be attached on array.Micro-porous adsorption layer c even application is on positive electrode material layer b surface.
as shown in Figure 3, the secondary aluminium cell described in this embodiment, it comprises battery container, is positioned over winding-structure in battery container and collector and collection ear; Wherein said winding-structure comprises the repetitive structure be made up of positive plate 1, barrier film 3 and negative plate 2 successively; Collector comprises positive collector 4 and negative collector 6; Collection ear comprises anode ear 5 and negative electrode lug 7.
embodiment 1
(1) preparation of graphene array: be placed in the quartz glass tube of tube type resistance furnace using 30 μm of thick nickel collectors as substrate, pass into argon gas and the hydrogen mixed gas of 1000sccm, wherein hydrogen volume ratio is 1%, is warming up to 650 DEG C simultaneously; Regulation voltage is to 10kV, produce stable glow plasma, after removing substrate surface impurity 10min, pass into 150sccm methane and 1350sccm argon gas, pass into steam simultaneously, control relative humidity 40%, then stop passing into argon gas and hydrogen mixed gas, reaction 20min, after terminating at reducing atmosphere borehole cooling to room temperature, obtained vertical orientated Graphene.
(2) composite sulfur: by the graphene array prepared and elemental sulfur in mass ratio 1:9 put into tube furnace, be heated to 155 DEG C, passing under condition of nitrogen gas, keep 10h, form the graphene array that load has sulphur.
embodiment 2
(1) preparation of graphene array: be placed in the quartz glass tube of tube type resistance furnace using 30 μm of thick nickel collectors as substrate, pass into argon gas and the hydrogen mixed gas of 1000sccm, wherein hydrogen volume ratio is 1%, is warming up to 650 DEG C simultaneously; Regulation voltage is to 10kV, produce stable glow plasma, remove substrate surface impurity, after 10min, pass into 150sccm methane and 1350sccm argon gas, pass into steam simultaneously, control relative humidity 40%, then stop passing into argon gas and hydrogen mixed gas, reaction 20min, after end at reducing atmosphere borehole cooling to room temperature, obtained vertical orientated Graphene.
(2) composite sulfur: by the graphene array prepared and elemental sulfur in mass ratio 1:9 put into tube furnace, be heated to 155 DEG C, passing under condition of nitrogen gas, keep 10h, form the graphene array that load has sulphur.
(3) preparation of superfine nano activated carbon fiber:
by (proportioning 80:20) 200g of methyl-sulfoxide and H2O mixed solvent; (mass ratio of acrylonitrile and itaconic acid is 98.5:1.5 to monomer; in solution, the mass fraction of total monomer is 18%); initator azobisisobutyronitrile (quality is 1.5% of total monomer quality) joins in Mitsui flask; put into thermostatical oil bath to heat; and keep temperature 60 C; magnetic agitation; and logical nitrogen protection; be polymerized 4 hours; by the white solid state thing cleaning of generation, filtration, vacuumize, grinding, obtain white polymer polyacrylonitrile powder.
polyacrylonitrile is dissolved in N, in N mono-dimethyl methyl phthalein amine, Keep agitation 24h, form homogeneous spinning solution, spinning solution is put into the needle tubing being equipped with 0.8mm, use driving pump with the speed extruding spinning stoste of 2.0mL/h, obtain more uniform ultrafine fiber felt.
the polyacrylonitrile-radical ultrafine fiber felt obtained is put into high-temperature blast drying oven, at 270 DEG C, pre-oxidation 30min, cooling room temperature, then puts into quartz ampoule, logical nitrogen, heating rate 20 DEG C/min, final temperature is 900 DEG C, then naturally drops to 100 DEG C, obtains the superfine nano carbon fiber of microcellular structure; Use electrical heating method, 800 DEG C.Activation 25min, under the steam activation condition that flow is 1mL/min, obtains superfine nano activated carbon fiber.
(4) preparation of micro-porous adsorption layer: the Kynoar solution of superfine nano active carbon fibre Wesy 10wt% is prepared into slip, wherein the mass ratio of sorbing material and described Kynoar solution is 8:2, in its solution of described Kynoar, solvent is 1-METHYLPYRROLIDONE, and spraying process prepares at anode active material layer surface the adsorption layer that a layer thickness is 5 ~ 8um.
embodiment 3
(1) preparation of carbon nano pipe array: take conductive paper of carbon fiber as substrate; Fe (NO3) 3 is catalyst, is coated in carbon paper surface in advance, take methane as carbon source; nitrogen is protection gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
(2) composite sulfur: by the carbon nano pipe array prepared and elemental sulfur in mass ratio 1:9 put into tube furnace, be heated to 155 DEG C, passing under condition of nitrogen gas, keep 10h, form sulphur/carbon nano-tube array composite material.
embodiment 4
(1) preparation of carbon nano pipe array: take conductive paper of carbon fiber as substrate, Fe (NO
3
)
3
for catalyst, being coated in carbon paper surface in advance, take methane as carbon source, and nitrogen is protection gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
(2) composite sulfur: by the carbon nano pipe array prepared and elemental sulfur in mass ratio 1:9 put into tube furnace, be heated to 155 DEG C, passing under condition of nitrogen gas, keep 10h, form sulphur/carbon nano-tube array composite material.
(3) preparation method of superfine nano activated carbon fiber is with the preparation method of superfine nano activated carbon fiber in embodiment 2.
(4) preparation of micro-porous adsorption layer: the Kynoar solution of superfine nano active carbon fibre Wesy 10wt% is prepared into slip, wherein the mass ratio of sorbing material and described Kynoar solution is 8:2, in its solution of described Kynoar, solvent is 1-METHYLPYRROLIDONE, and spraying process prepares at anode active material layer surface the adsorption layer that a layer thickness is 5 ~ 8um.
embodiment 5
prepared by embodiment 1,2,3,4 positive pole live be cut into 40mm wide × the long pole piece of 15mm, the barrier film thick with 0.16mm and be wound into battery core with aluminium flake as the negative pole that negative active core-shell material is made and load nickel plating box hat, reinject electrolyte, and secondary aluminium cell is made in sealing.
embodiment 6
carry out charge and discharge cycles test to made battery, charge to 2.8V, cut-ff voltage is 1.2 V, and test result is as follows:
although be described in detail the utility model with reference to embodiment, but those skilled in the art is to be understood that, when the design of the present utility model do not departed from described in appended claims and equivalent thereof and scope, various amendment and replacement can be made to it.
Claims (7)
1. an anode pole piece, comprises conductive substrates and positive electrode material layer, it is characterized in that, described anode pole piece also comprises the micro-porous adsorption layer be coated on positive electrode material layer.
2. anode pole piece as claimed in claim 1, it is characterized in that, described conductive substrates is the metals or nonmetal such as carbon paper, carbon fiber, nickel, aluminium, iron, copper, zinc, lead, manganese, conductive plastics, conductive rubber or highly doped silicon.
3. anode pole piece as claimed in claim 1, it is characterized in that, described positive electrode material layer is made up of conductive array and the active material sulphur be attached on array, have three-dimensional conductive network configuration, and vertical-growth is in conductive substrates.
4. anode pole piece as claimed in claim 2, is characterized in that, described conductive array is any one in carbon nano pipe array, graphene array or carbon fiber array.
5. anode pole piece as claimed in claim 1, it is characterized in that, described micro-porous adsorption layer is made up of sorbing material and binding agent, and thickness is 5 ~ 8 μm.
6. anode pole piece as claimed in claim 5, it is characterized in that, described sorbing material is superfine nano activated carbon fiber, and fibre diameter is Nano grade, and specific area is 1000 ~ 1300m
2/ g, Micropore volume is 0.4 ~ 0.45cm
3/ g, micro-pore diameter is 0.54 ~ 0.66nm.
7. a secondary aluminium cell, comprise battery container and be positioned at battery core assembly and the electrolyte of battery container inside, battery core assembly comprises the anode pole piece, barrier film and the cathode pole piece that stack gradually, it is characterized in that, described anode pole piece is anode pole piece according to claim 1, cathode pole piece is the active material containing aluminium, and electrolyte is that non-water is containing aluminium electrolyte.
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| CN201420669451.XU CN204156016U (en) | 2014-11-11 | 2014-11-11 | A kind of anode pole piece and secondary cell |
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|---|---|---|---|
| CN201420669451.XU CN204156016U (en) | 2014-11-11 | 2014-11-11 | A kind of anode pole piece and secondary cell |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107994207A (en) * | 2016-10-26 | 2018-05-04 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and cathode plate thereof |
| CN111974338A (en) * | 2019-05-23 | 2020-11-24 | 宁德时代新能源科技股份有限公司 | Gas adsorbent capable of prolonging service life of lithium ion battery and lithium ion battery thereof |
| CN113161516A (en) * | 2021-02-24 | 2021-07-23 | 东莞塔菲尔新能源科技有限公司 | Lithium ion battery |
-
2014
- 2014-11-11 CN CN201420669451.XU patent/CN204156016U/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107994207A (en) * | 2016-10-26 | 2018-05-04 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and cathode plate thereof |
| CN107994207B (en) * | 2016-10-26 | 2020-07-31 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and cathode plate thereof |
| CN111974338A (en) * | 2019-05-23 | 2020-11-24 | 宁德时代新能源科技股份有限公司 | Gas adsorbent capable of prolonging service life of lithium ion battery and lithium ion battery thereof |
| WO2020233264A1 (en) * | 2019-05-23 | 2020-11-26 | 宁德时代新能源科技股份有限公司 | Gas adsorbent, secondary battery and device |
| CN113161516A (en) * | 2021-02-24 | 2021-07-23 | 东莞塔菲尔新能源科技有限公司 | Lithium ion battery |
| CN113161516B (en) * | 2021-02-24 | 2024-01-09 | 江苏正力新能电池技术有限公司 | Lithium ion battery |
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| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150211 Termination date: 20191111 |
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| CF01 | Termination of patent right due to non-payment of annual fee |