CN103500865A - Lithium-cathode semi-fuel cell component - Google Patents

Lithium-cathode semi-fuel cell component Download PDF

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Publication number
CN103500865A
CN103500865A CN201310489161.7A CN201310489161A CN103500865A CN 103500865 A CN103500865 A CN 103500865A CN 201310489161 A CN201310489161 A CN 201310489161A CN 103500865 A CN103500865 A CN 103500865A
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lithium
cathode
anode
fuel cell
housing
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CN201310489161.7A
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CN103500865B (en
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汪长安
刘凯
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Tsinghua University
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Tsinghua University
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

A lithium-cathode semi-fuel cell component comprises a cathode housing. A copper liner is fastened into the cathode housing. A conical hole of the copper liner aligns to a screw hole on the cathode housing to form a lithium adding passage. A copper screw is screwed into the screw hole of the cathode housing. A first round magnet and a copper-plated round iron are attracted together, and the magnet is inwardly arranged in the copper liner. A second round magnet is mounted in a fastening groove at the bottom of the cathode housing. A cell anode is mounted in a cavity of an anode housing. According to needs, an anode lead and an anode joint are arranged in a hole on the anode housing to form an electrolyte circulating access or gas access. A rubber gasket and a solid-state lithium ion conductor are sequentially backed between the cathode housing and the anode housing and are coated by epoxy resin glue, and the cathode housing and the anode housing are connected in a threaded manner and can be used for assembling a lithium-cathode semi-fuel cell so as to effectively protect and quickly mechanically charge lithium cathode, and further, operation is simple.

Description

A kind of cathode of lithium semi-fuel cell assembly
Technical field
The present invention relates to new forms of energy cathode of lithium semi-fuel cell technical field, be specifically related to a kind of cathode of lithium semi-fuel cell assembly.
Background technology
The worry of lack of energy and environmental pollution is impelled to the countries in the world electric automobile of all going into overdrive to research and develop, and the key of good electric automobile is high-performance power battery, comprising: large capacity, macro-energy density, charging interval are short, long service life, cost is reasonable and safe and reliable etc.Little than capacity density, capacity is little or, containing the conventional batteries of the easy contaminated environment of heavy metal, the lithium of energy density super large-empty battery and the great fuel cell of capacity are considered to the most promising power in environmental protection battery.The fuel cell development better, obtained practical application, but its structure is more complicated, and energy density is still less than normal.Lithium-empty battery is novel battery, in the laboratory research stage, also has a lot of problems to need to solve, such as: (1) is affected by anodal blocking effect, and actual energy density is far below theoretical value; (2) cycle performance is poor, and in cyclic process, electrolyte decomposes, and has Li dendrite to form, and the battery capacity decay is serious; (3) the same with conventional batteries, the charging interval is long etc.
The cathode of lithium semi-fuel cell be take lithium metal as negative pole, serves as fuel, and anodal oxidant is dissolved in anode electrolyte.During operation, the anode electrolyte circular flow is crossed electrode, and in time supplemental oxidant is advanced electrolyte, and mechanical charge again after the negative pole lithium metal runs out of, add new lithium metal.Cathode of lithium semi-fuel cell negative pole has the characteristics of lithium battery, is just having the characteristics of fuel cell, is the combination of the two, also has the advantage of the two concurrently:
(1) high voltage and high-energy-density.Act as a fuel, lithium metal has the energy density suitable with gasoline, and its electrode potential is minimum in all metals, therefore uses lithium metal as negative pole, and the cathode of lithium semi-fuel cell of composition is the same with lithium battery, has high voltage and high-energy-density.
(2) can the Quick mechanical charging.After battery discharge is complete, by mechanical charge fast, directly in battery, add new lithium metal, battery just can discharge again.The mechanical charge pattern has shortened the charging interval greatly, make it almost can add the oil phase analogy with gasoline engine, and the electrolyte of having avoided high-voltage charge to bring decomposes and the Li dendrite growth question.
(3) capacity is large.Similar with fuel cell, the capacity of cathode of lithium semi-fuel cell depends on the amount of the fuel of storage, and fuel can be stored in the outer fuel storage tank of battery, and therefore, the capacity of battery can be done very greatly.
(4) the battery power output can be regulated easily.Similar with fuel cell, can carry out regulating cell power by regulating positive active material flow velocity and concentration.
Because have above advantage, the cathode of lithium semi-fuel cell is the more satisfactory selection of following batteries of electric automobile.Assemble the cathode of lithium semi-fuel cell, protect closely lithium metal, in order to avoid it contacts with water, air etc. and be corroded, mechanical charge easily again, therefore need specially designed battery component simultaneously.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of cathode of lithium semi-fuel cell assembly, can protect well lithium anode, the while is mechanical charge easily.
In order to achieve the above object, the technical scheme that the present invention takes is:
A kind of cathode of lithium semi-fuel cell assembly, comprise negative pole housing 2, and copper liner 6 is sticked in negative pole housing 2, and the bellmouth of copper liner 6 is aimed at the screw on anode coat 2, forms and add the lithium passage, and brass screw 9 is screwed in the screw of anode coat 2; Together with justifying magnet 7 and copper facing round iron sheet 10 is inhaled first, and magnet inwardly, puts in copper liner 6, and other one second round magnet 8 is contained in the draw-in groove of anode coat 2 bottoms;
Anode 4 is contained in anodal shell 1 cavity, and positive wire 13, one or two first positive terminal 3, the second positive terminal 14 are loaded onto in the hole on anodal shell 1, to form circulate electrolyte, imports and exports or gas inlet and outlet;
Pad successively upper the first rubber sheet gasket 11, solid lithium ion conductors 5, the second rubber sheet gasket 12 in the middle of negative pole housing 2 and anodal shell 1, and be coated with epoxide-resin glue, anodal shell 1 and anode coat 2 are threaded.
Described anode coat 2 adopts the Teflon material, with 6 lightpressure fits of copper liner; When brass screw 9 is tightened, under screw, edge props up the bellmouth hole wall of copper liner 6.
Described copper liner 6 and copper facing round iron sheet 10 are slidably matched.
Described anodal shell 1 adopts the Teflon material.
Described the first positive terminal 3, the second positive terminal 14 adopt the Teflon material.
The present invention has designed a kind of new battery component, can be for assembling the cathode of lithium semi-fuel cell, realize effective protection of cathode of lithium and mechanical charge fast, and simple to operate.Utilize this battery component, successfully assembled lithium-hydrogen peroxide semi-fuel cell in laboratory, " mechanical charge-electric discharge " cycle characteristics of battery is studied.Result verification the reliability of battery component.
The accompanying drawing explanation
Fig. 1 is explosive view of the present invention (oxidant used is liquid situation).
The structural representation that Fig. 2 is anode coat of the present invention, the profile that Fig. 2 (a) is anode coat, the end view that Fig. 2 (b) is anode coat.
The structural representation that Fig. 3 is copper liner of the present invention, the profile that Fig. 3 (a) is the copper liner, the end view that Fig. 3 (b) is the copper liner.
Fig. 4 is copper facing iron wafer architecture schematic diagram of the present invention, and Fig. 4 (a) is the front view of copper facing iron disk, and Fig. 4 (b) is the end view of copper facing iron disk.
Fig. 5 is the anodal shell mechanism schematic diagram of the present invention.
Fig. 6 is positive terminal structural representation of the present invention.
Fig. 7 is the lithium-operation of hydrogen peroxide semi-fuel cell and testing apparatus schematic diagram.
Fig. 8 is lithium-hydrogen peroxide semi-fuel cell mechanical charge-discharge cycles curve.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
With reference to Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6, a kind of cathode of lithium semi-fuel cell assembly, comprise negative pole housing 2, copper liner 6 is sticked in negative pole housing 2, the bellmouth of copper liner 6 is aimed at the screw on anode coat 2, forms and adds the lithium passage, and brass screw 9 is screwed in the screw of anode coat 2; Together with justifying magnet 7 and copper facing round iron sheet 10 is inhaled first, and magnet inwardly, puts in copper liner 6, and other one second round magnet 8 is contained in the draw-in groove of anode coat 2 bottoms;
Anode 4 is contained in anodal shell 1 cavity, and as required, positive wire 13, one or two first positive terminal 3, the second positive terminal 14 are loaded onto in the hole on anodal shell 1, to form circulate electrolyte, imports and exports or gas inlet and outlet;
Pad successively upper the first rubber sheet gasket 11, solid lithium ion conductors 5, the second rubber sheet gasket 12 in the middle of negative pole housing 2 and anodal shell 1, and be coated with epoxide-resin glue, anodal shell 1 and anode coat 2 are threaded, and through above operation, battery component has just assembled.
Described anode coat 2 adopts the Teflon material, with 6 lightpressure fits of copper liner; When brass screw 9 is tightened, under screw, along the bellmouth hole wall that props up copper liner 6, keep good electrically contacting.
Described copper liner 6 and copper facing round iron sheet 10 are slidably matched.
Described anodal shell 1 adopts the Teflon material.
Described the first positive terminal 3, the second positive terminal 14 adopt the Teflon material.
Operation principle of the present invention is:
The battery component assembled is taken in the argon shield glove box, and the first circle magnet 7 is inhaled mutually with the second circle magnet 8, and copper facing round iron sheet 10 is restricted to anode coat 2 bottoms, adds the lithium passage unobstructed.By a certain amount of lithium particle, from add the lithium passage, be added in the negative pole cavity, and drip appropriate organic electrolyte, the second circle magnet 8 in upset anode coat 2 draw-in grooves, the first circle magnet 7 and the second circle magnet 8 repel each other, copper facing round iron sheet 10 is advanced, the lithium particle is just compacted, and keeps good electrically contacting with copper facing round iron sheet 10.Finally tighten brass screw 9, and apply a small amount of fluid sealant.Battery has completed machinery and has added lithium, can from glove box, take out, in aerial discharge.Positive electrode, anode electrolyte and oxidant can be selected as required.With reference to Fig. 5, if with liquid oxidizer (as hydrogen peroxide solution, ferric ion solutions etc.), can seal Ф 1 hole of anodal shell 1, positive electrode is placed in anodal shell 1 cavity, positive wire 13 is connected with positive electrode and draws from Ф 3 holes, anodal shell 1 two remaining screws can be used as the import and export of liquid electrolyte, the use that the electrolysis liquid recycle stream is moving; If with gaseous oxidizer (as oxygen etc.), gaseous state electrode and positive wire 13 can be placed in to the large screw of anodal shell 1 bottom, lead-in wire is drawn from Ф 1 hole, tightening the large size positive terminal fixes gaseous state electrode and positive wire, with reference to Fig. 6, gaseous oxidizer can enter the gaseous state electrode from Ф 2 holes of large size positive terminal, the moving use of remaining two screw electrolysis liquid recycle streams.As changed positive electrode, as long as turn on the large size positive terminal, from the rear portion of anodal shell, change and get final product, and without taking battery apart.After battery discharge is complete, battery is moved into to glove box, back out brass screw 9, upset circle magnet sucks back copper facing round iron sheet 10, add the lithium particle, upset circle magnet advances copper facing round iron sheet 10 to compress the lithium particle, tightens brass screw 9, apply fluid sealant, battery has just completed mechanical charge, can again discharge.
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment
Assembled lithium-hydrogen peroxide semi-fuel cell with above-mentioned battery component.Wherein, select and be dissolved with 1mol/L LiPF 6eC, DEC(volume ratio be 1:1) the mixed solution organic electrolyte; (principal crystalline phase is Li to the LISICON sheet of buying from Japanese Ohara company 1+x+yal x(Ti, Ge) 2-xsi yp 3-yo 12, diameter 15mm, thickness 150 μ m, under room temperature, lithium ion conductivity 1 * 10 -4scm -1) as solid lithium ion conductors; With nickel foam (1cm * 1cm * 0.5mm, 110PPI, 300g/m 2) do positive electrode; 2mol/L LiCl solution is anode electrolyte; Oxidant hydrogen peroxide is added in LiCl electrolyte.Battery operation and testing apparatus are as shown in Figure 7.
With the electric battery test system of indigo plant (CT2001A5V/10mA), battery is carried out to the test of " mechanical charge-electric discharge " cycle performance, in discharge process, under the peristaltic pump effect, anode electrolyte flows through foam nickel anode with the rate loop of 10mL/min, drip 30% hydrogen peroxide solution aperiodically in LiCl electrolyte, to maintain hydrogen peroxide concentration, discharging current is 0.1mA, and the discharge curve obtained as shown in Figure 8.
Within the testing time of 700 hours, carried out altogether mechanical charge 4 times, obtained 4 discharge curves, discharge voltage is substantially steady, and discharge platform is obvious, and open circuit voltage is 3.0V, and average discharge volt is 2.7V.Result shows that the lithium-hydrogen peroxide semi-fuel cell of assembling has good stability.About 10 minutes consuming time of mechanical charge after being discharged, very convenient.
Obtain according to the Mass Calculation of the lithium metal of adding battery the electric weight that can emit in theory, with actual comparision of quantity of electricity of emitting, draw the lithium metal utilance, result is as shown in table 1.
Table 1 lithium-hydrogen peroxide semi-fuel cell lithium metal utilance
Average lithium metal utilance reaches 80.9%, illustrates that battery module structure can stop air, aqueous vapor etc. to infilter the negative pole chamber substantially, has protected well lithium metal, and during electric discharge, the side reactions such as corrosion of lithium seldom.The lithium metal utilance does not yet increase and reduces with " mechanical charge-electric discharge " cycle-index, at least in front four circulations, there is no capacity attenuation.

Claims (5)

1. a cathode of lithium semi-fuel cell assembly, comprise negative pole housing (2), it is characterized in that: copper liner (6) is sticked in negative pole housing (2), the bellmouth of copper liner (6) is aimed at the screw on anode coat (2), formation adds the lithium passage, and brass screw (9) is screwed in the screw of anode coat (2); The first circle magnet (7) and copper facing round iron sheet (10) are inhaled together, and magnet inwardly, put in copper liner (6), other one second round magnet (8) is contained in the draw-in groove of anode coat (2) bottom;
Anode (4) is contained in anodal shell (1) cavity, positive wire (13), one or two first positive terminal (3), the second positive terminal (14) are loaded onto in hole on anodal shell (1), to form circulate electrolyte, import and export or gas inlet and outlet;
Pad successively upper the first rubber sheet gasket (11), solid lithium ion conductors (5), the second rubber sheet gasket (12) in the middle of negative pole housing (2) and anodal shell (1), and be coated with epoxide-resin glue, anodal shell (1) and anode coat (2) are threaded.
2. a kind of cathode of lithium semi-fuel cell assembly according to claim 1 is characterized in that: described anode coat (2) adopts the Teflon material, with copper liner (6) lightpressure fit; Brass screw (9) is while tightening, and under screw, edge props up the bellmouth hole wall of copper liner (6).
3. a kind of cathode of lithium semi-fuel cell assembly according to claim 1, it is characterized in that: described copper liner (6) and copper facing round iron sheet (10) are slidably matched.
4. a kind of cathode of lithium semi-fuel cell assembly according to claim 1, is characterized in that: described anodal shell (1) employing Teflon material.
5. a kind of cathode of lithium semi-fuel cell assembly according to claim 1, is characterized in that: described the first positive terminal (3), the second positive terminal (14) employing Teflon material.
CN201310489161.7A 2013-10-18 2013-10-18 A kind of Lithium-cathode semi-fuel cell component Active CN103500865B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108768288A (en) * 2018-06-15 2018-11-06 浙江晶科能源有限公司 A kind of wire box applied to photovoltaic module

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US20030124418A1 (en) * 2002-01-03 2003-07-03 Dow Eric G. Separated flow liquid catholyte aluminum hydrogen peroxide seawater semi fuel cell
CN101242017A (en) * 2007-12-28 2008-08-13 中国航天科技集团公司第六研究院第十一研究所 Half fuel cell
CN201134482Y (en) * 2007-12-25 2008-10-15 中国航天科技集团公司第六研究院第十一研究所 Semi-fuel cell of aluminum/peroxide
CN102938481A (en) * 2012-11-09 2013-02-20 中国电子科技集团公司第十八研究所 High-energy low-consumption Al-H2O2 semi-fuel cell
CN103000970A (en) * 2012-11-09 2013-03-27 中国电子科技集团公司第十八研究所 Ion exchange membrane for Al-H2O2 semi-fuel cell and cell using same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030124418A1 (en) * 2002-01-03 2003-07-03 Dow Eric G. Separated flow liquid catholyte aluminum hydrogen peroxide seawater semi fuel cell
CN201134482Y (en) * 2007-12-25 2008-10-15 中国航天科技集团公司第六研究院第十一研究所 Semi-fuel cell of aluminum/peroxide
CN101242017A (en) * 2007-12-28 2008-08-13 中国航天科技集团公司第六研究院第十一研究所 Half fuel cell
CN102938481A (en) * 2012-11-09 2013-02-20 中国电子科技集团公司第十八研究所 High-energy low-consumption Al-H2O2 semi-fuel cell
CN103000970A (en) * 2012-11-09 2013-03-27 中国电子科技集团公司第十八研究所 Ion exchange membrane for Al-H2O2 semi-fuel cell and cell using same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108768288A (en) * 2018-06-15 2018-11-06 浙江晶科能源有限公司 A kind of wire box applied to photovoltaic module
CN108768288B (en) * 2018-06-15 2024-04-26 浙江晶科能源有限公司 Line box applied to photovoltaic module

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