CN105304922B - A kind of sea-bottom deposit nitride layer reactive metal fuel battery structure and device - Google Patents
A kind of sea-bottom deposit nitride layer reactive metal fuel battery structure and device Download PDFInfo
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- CN105304922B CN105304922B CN201410298739.5A CN201410298739A CN105304922B CN 105304922 B CN105304922 B CN 105304922B CN 201410298739 A CN201410298739 A CN 201410298739A CN 105304922 B CN105304922 B CN 105304922B
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Abstract
The invention patent discloses a kind of sea-bottom deposit nitride layer reactive metal fuel battery structure and device, its structure feature is: using active metal as cell negative electrode material, it is placed in the sea-bottom deposit nitride layer of certain depth, conductive carbon material is placed in sea water layer as anode, sea-bottom deposit nitride layer/seawater bed boundary is used for inside battery ionic conduction as natural amberplex;Positive and negative electrode is drawn by conducting wire respectively to be connected with the instrument of a fixed load, constitutes cell circuit and Open architecture.Wherein active metal provides electronics, carbon material obtains electronics and reduction reaction occurs for Dissolved Oxygen in Seawater as donor.The battery structure utilizes anoxic, anaerobism and the closed characteristic of sea-bottom deposit nitride layer, both the self-corrosion reaction of negative metal had been slowed down, it avoids surface metal from generating passivating film to cause to be passivated, slow down passivation caused by positive electrode surface inorganic deposition again, the whole stability for keeping battery positive and negative electrode performance and long-life, are a kind of good underwater power sources.
Description
Technical field
The invention patent relates to a kind of underwater chemical fuel cell power supplys, are with sea-bottom deposit nitride layer more particularly to one kind
The reactive metal fuel battery structure and device of electrolyte environment.
Background technique
Fuel cell is 21 century important clean efficiency power generation technology, and there are many kinds of fuel cells, including solid oxidation
Object fuel cell, molten carbonate fuel cell, phosphoric acid fuel cell, direct methanol fuel cell, pem fuel electricity
Pond etc..It wherein is also known as metal fuel battery by the fuel cell of fuel of metal, several light metals of aluminium, magnesium, zinc, lithium are because of its tool
The very high chemical activity having, is considered as ideal negative electrode material.But when due to electric discharge, there is hydrogen precipitation, be generally difficult to
Aqueous systems closed structure, and open cell structure is mostly used to design.This open cell structure can not only produce reaction
Outside object and waste heat discharge battery, seawater can also be introduced directly into and serve as electrolyte solution, and when seabed works, be not necessarily to resistance to compression
Shell designs convenient for structure.Therefore, using above-mentioned active metal or alloy as the seawater metal fuel battery (letter of negative electrode material
Claim seawater battery) be always underwater power source research hotspot.Seawater battery is during second of world war by U.S. Bell
Lab design, General Electric Co. Limited develop, it is provided by the corrosion dissolution of anode (cathode) metal material in the seawater
Discharge current, and cathode (anode) then relies primarily on dissolved oxygen of seawater and carries out reduction reaction offer yin on inert electrode
(in primary battery field, often electrode is referred to as positive and negative electrode to people to electrode current, and electrochemistry and electrolytic cell field, people's electrode are referred to as
Cathode and anode).The most prominent feature of seawater battery is not need to carry electrolyte, can utilize natural sea-water when needed
Form electrolyte.
Seawater battery is structurally characterized in that: metal negative electrode and conductive carbon material anode are placed in seawater electrolysis matter, are kept
One relatively-stationary distance, the cathode of seawater battery mainly provide electronics, and metal oxidation reaction occurs, and anode mainly occurs molten
Oxygen reduction reaction is solved, by taking magnesium as an example, positive and negative electrode reaction is as follows respectively:
Cathode: Mg-2e- →Mg2+, anode: O2+2H2O+e-→4OH-,
Seawater battery always exists a large amount of problems in engineer application.Such as: positive inorganic sediments passivation, according to
Above-mentioned positive and negative electrode reaction product, in battery During Process of Long-term Operation, magnesium ion is easy and hydroxide ion generates magnesium hydroxide and sinks
It forms sediment, positive electrode surface generates a large amount of inorganic sediments, and magnesium hydroxide is non-conductive, leads to positive failure;Equally, aluminium ion can also give birth to
At the cotton-shaped deposition of aluminium hydroxide, cathode performance is seriously affected.Another example is: metallic aluminium, magnesium anode material surface be under aerobic conditions,
Surface is readily generated passivating film (pellumina, magnesium oxide films), and pellumina is very stable, and cathode is caused seriously to be passivated, and influences
Metal ejected electron and battery performance.In another example magnesium metal, aluminium, zinc are very active, it is easy to happen evolving hydrogen reaction in the seawater, causes
Serious self-corrosion also easily causes serious chemical attack and electrochemical corrosion under ocean current souring, these are influenced
The stability of seawater battery service life and battery.
With the continuous development expanded with deep-sea detecting of mankind's ocean development range, underwater sensor, underwater robot
Equal instruments are the important equipments that people carry out ocean research, and the work of these instruments then needs continuous power drives, also,
Need to be distributed in far-reaching extra large position for monitoring environmental physics, chemokines variation.Many electronic instruments need continuous permanent worker
Make (up to the several years or longer), during desired work, once being exhausted using self-powered, they will be lost accordingly
Use function.Currently, people common several supply power mode (e.g., lead-acid accumulator, solar battery, high-energy lithium batteries
Pond, the on the bank cable transfer etc. of power supply) it cannot be long-term by influence factors such as subsea cryogenic, high pressure, weather, long transmission distances
Stablize and power supply is provided, it is difficult to meet the requirement detected for a long time at a distance.Still there is an urgent need to study underwater power supply with full
The demand of sufficient ocean development and detection.
Summary of the invention
Sea-bottom deposit nitride layer is a kind of special electrolyte environment, can be used for submarine sedimentary strata reactive metal fuel battery
Design.Sea-bottom deposit nitride layer (abbreviation ooze) connects with sea water layer, is rich in natural electrolytes, and good conductivity resistance is small;Meanwhile sea
The natural interface of mud/seawater is a kind of natural amberplex, can be realized the ion exchange of submarine sedimentary strata and seawater, is realized
Inside battery ionic conduction;Active metal is placed in sea-bottom deposit nitride layer, can be acted on to avoid the erosion corrosion of ocean current;Seabed is heavy
Since bacterial metabolism acts on inside product nitride layer, inside keeps anoxic and anaerobic environment, this special enclosed environment to be conducive to keep away
Exempt from or slow down the generation of active metal surface passivated membrane;The sealing process of submarine sedimentary strata can inhibit the diffusion of metal ion,
Anode inorganic sediments is reduced, is conducive to battery performance and stablizes;Organic matter generates acid, acyclic acidic in bacterial metabolism sedimentary
Border can also generate deposit to avoid metal surface.
In view of the particularity and technical advantage of above-mentioned submarine sedimentary strata, in order to overcome seawater battery the deficiencies in the prior art,
The invention patent provides a kind of sea-bottom deposit nitride layer reactive metal fuel battery structure, and active metal is placed in bottom sediment
In layer, in the seawater, structure is simple for positive carbon material work, low in cost, is easy to lay and fix, both reduces negative electrode material
Self-corrosion also reduces the inorganic sediments passivation of positive electrode, keeps battery performance to stablize, extend battery, this is right
It is of great significance in the supply long-term to oceanographic instrumentation power supply.
Technical solution used by the invention patent is:
A kind of sea-bottom deposit nitride layer reactive metal fuel battery structure and device, structure feature are: being made with active metal
It for the negative electrode material of battery, is placed in the sea-bottom deposit nitride layer of certain depth, conductive carbon material is placed in seawater as anode, sea
Bottom sediments nitride layer/seawater bed boundary is used for inside battery ionic conduction as natural amberplex;Positive and negative electrode leads to respectively
It crosses conducting wire extraction to be connected with the instrument of a fixed load, constitutes cell circuit and open cell device.
As shown in Figure 1, the battery structure specifically includes that active metal cathode 7(such as aluminium, magnesium, zinc, iron and its alloy), lead
Electrical carbon material anode 2(such as carbon plate, carbon fiber, carbon felt, carbon cloth etc.), sea-bottom deposit nitride layer 6, sea water layer 3, sea-bottom deposit nitride layer/
Seawater bed boundary 5, external circuit 2 and load 1.Wherein main structure feature is that metal negative electrode is placed in sea-bottom deposit nitride layer,
Using bottom sediment as conducting electrolyte, anode is placed in seawater, using seawater as conducting medium.The battery structure and device are whole
Stability and the long-life that positive and negative electrode performance is kept on body, are a kind of good underwater power sources, for driving underwater monitoring instrument
Longtime running.
Compared with prior art, the beneficial effect of the invention patent and technical advantage are as follows:
1, the cell apparatus advantageously reduces or avoids the inorganic deposition of anode, reduces anode passivation, keeps just
The electric conductivity and stability in use of pole, this is because submarine sedimentary strata can stop negative metal ion to be diffused into seawater.
2, the cell apparatus is conducive to that active metal is avoided to be washed away by ocean current, slow down active metal electrochemical corrosion and
Chemical attack extends the service life of metal electrode and entire battery.
3, since bacterial metabolism acts on, anaerobic environment and acidic environment, this environmental benefits are kept inside submarine sedimentary strata
In the formation that metal oxide film surface is reduced or avoided, the passivation of metal is reduced, keeps the stability and continuous discharge energy of electrode
Power is conducive to extend using battery life.
4, due to anaerobic environment in submarine sedimentary strata, current potential is significantly lower than seawater current potential (containing dissolved oxygen), activity gold
Category is inserted into sedimentary, and battery cathode current potential is that metal current potential is added with the current potential that sedimentary anaerobism reduces, the battery structure
Output voltage with higher.
5, in active metal merging submarine sedimentary strata, be conducive to cell apparatus being stabilized in seabed, avoid in ocean current
Under long term, cell apparatus lodges.
6, this cell apparatus is not only using submarine sedimentary strata and seawater as conducting electrolyte, but also utilizes sedimentary/sea water layer
Inner conductive is realized as amberplex in interface, and this Open architecture avoids the design of seabed pressure-tight, battery structure
Simply, cost is relatively low.
7, entire cell apparatus and weight can be used as the counterbalance design of underwater monitoring instrument, be conducive to seabed work and cloth
It puts.
Detailed description of the invention
Figure one, sea-bottom deposit nitride layer reactive metal fuel battery structure and device figure
1. load;2. dispatch from foreign news agency line conductor;3. sea water layer;4. conductive carbon material is positive;
5. sea-bottom deposit nitride layer/seawater bed boundary;6. sea-bottom deposit nitride layer;7. negative electrode active metal.
Specific embodiment
The invention patent is further illustrated with reference to the accompanying drawing.
Embodiment 1:
As shown in Figure 1, active metal cathode 7 selects 50 mm of diameter, the AZ31 magnesium alloy of 500 mm of length squeezes out stick,
The drilling of magnesium bar end center location, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects conductive carbon fibre
Multiple titanium carbon fiber brushes are welded on a rectangular or round titanium frame by the carbon fiber brush being wound with 1mm titanium silk,
Leading-out copper wire, and keep copper wire extraction location waterproof sealing.The conducting wire lead-out wire 2 of anode and cathode connects a 10-1000
The ohmic load 1 of ohm, resistance and electrode extraction wire also need sealing waterproof and connect.Cathode magnesium bar 7 is inserted into seabed
In deposit layer (ooze) 6, positive titanium carbon fiber brush frame 4 and ohmic load 1 are placed in sea water layer 3, obtain sea-bottom deposit
Nitride layer magnesium fuel cell.The output voltage of the battery is 1.7-2.1V, and voltage is different and different with load.
Embodiment 2:
As shown in Figure 1, active metal cathode 7 selects 20 mm of diameter, the AZ61 magnesium alloy of 400 mm of length squeezes out stick,
The drilling of magnesium bar end center location, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects conductive carbon fibre
Multiple titanium carbon fiber brushes are welded on a rectangular or round titanium frame by the carbon fiber brush being wound with 1mm titanium silk,
Leading-out copper wire, and keep copper wire extraction location waterproof sealing.The conducting wire lead-out wire 2 of anode and cathode connects a 10-1000
The ohmic load 1 of ohm, resistance and electrode extraction wire also need sealing waterproof and connect.Cathode magnesium bar 7 is inserted into seabed
In deposit layer (ooze) 6, positive titanium carbon fiber brush frame 4 and ohmic load 1 are placed in seawater 3, obtain bottom sediment
Layer magnesium fuel cell.The output voltage of the battery is 1.7-2.1V, and electric current is different and different with load.
Embodiment 3:
As shown in Figure 1, active metal cathode 7 selects 50 mm of diameter, the AZ31 magnesium alloy of 500 mm of length squeezes out stick,
The drilling of magnesium bar end center location, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects 1 mm2It is conductive
Conductive carbon cloth surfaces are connected copper conductor, and carbon cloth are fixed on a rectangular or round titanium frame by carbon cloth production.Anode
One 10-1000 ohm of ohmic load 1 is connected with the conducting wire lead-out wire 2 of cathode, resistance and electrode extraction wire also need
Seal waterproof connection.Cathode magnesium bar 7 is inserted into sea-bottom deposit nitride layer (ooze) 6, positive titanium carbon fiber brush frame 4 and electricity
Resistance load 1 is placed in seawater 3, obtains submarine sedimentary strata magnesium anode fuel cell.The output voltage of the battery is 1.7-2.1V, electricity
Stream is different and different with load.
Embodiment 4:
As shown in Figure 1, selection 50 mm of diameter of active metal cathode 7, the AI-1 high activity aluminium alloy bars of 500 mm of length,
It drills in end center location, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects conductive carbon fibres peacekeeping
Multiple titanium carbon fiber brushes are welded on a rectangular or round titanium frame by the carbon fiber brush that 1 mm titanium silk is wound,
Leading-out copper wire, and keep copper wire extraction location waterproof sealing.The conducting wire lead-out wire 2 of anode and cathode connects a 10-1000
The ohmic load 1 of ohm, resistance and electrode extraction wire also need sealing waterproof and connect.Cathode aluminium bar 7 is inserted into seabed
In deposit layer (ooze) 6, positive titanium carbon fiber brush frame 4 and ohmic load 1 are placed in seawater 3, obtain bottom sediment
Layer aluminium fuel cell.The output voltage of the battery is that 1.5-1.9V(aluminium alloy is different, and operating potential is different), electric current with load not
It is same and different.
Embodiment 5:
As shown in Figure 1, selection 50 mm of diameter of active metal cathode 7, the AI-1 high activity aluminium alloy bars of 500 mm of length,
It drills in end center location, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects 1.0 mm2It is conductive
Conductive carbon cloth face seal is connected copper conductor, and carbon cloth is fixed on a rectangular or round titanium frame by carbon cloth production.
The conducting wire lead-out wire 2 of anode and cathode connects one 10-1000 ohm of ohmic load 1, and resistance and electrode extraction wire are same
Need to seal waterproof connection.Cathode aluminium bar 7 is inserted into sea-bottom deposit nitride layer (ooze) 6, positive titanium carbon fiber brush frame 4
It is placed in seawater 3 with ohmic load 1, obtains sea-bottom deposit nitride layer aluminium fuel cell.The output voltage of the battery is 1.5-1.9V
(aluminium alloy is different, and aluminium operating potential is different), electric current is different and different with load.
Embodiment 6:
As shown in Figure 1, active metal cathode 1 selects 50 mm of diameter, the ZT-1 kirsite stick of 500 mm of length, in end
Center location drilling, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects 1.0 mm2Conductive carbon is fabric
Make, conductive carbon cloth face seal is connected into copper conductor, and carbon cloth is fixed on a rectangular or round titanium frame.Anode and
The conducting wire lead-out wire 2 of cathode connects one 10-1000 ohm of ohmic load 1, and resistance and electrode extraction wire also need close
Seal waterproof connection.Cathode zinc bar 7 is inserted into sea-bottom deposit nitride layer (ooze) 6, positive titanium carbon fiber brush frame 4 and resistance
Load 1 is placed in sea water layer 3, obtains sea-bottom deposit nitride layer Zinc fuel battery.The output voltage of the battery is the conjunction of 1.0-1.3V(zinc
Golden different, operating potential is different), electric current is different and different with load.
Embodiment 7:
As shown in Figure 1, active metal cathode 7 selects 50 mm of diameter, the ZT-1 kirsite stick of 500 mm of length, in end
Center location drilling, is inserted into copper wire, is sealed using waterproof gasket cement, prevent leak.Anode 4 selects conductive carbon fibres peacekeeping 1mm titanium
The carbon fiber brush that silk is wound, multiple titanium carbon fiber brushes are welded on a rectangular or round titanium frame, draw copper
Line, and keep copper wire extraction location waterproof sealing.The conducting wire lead-out wire 2 of anode and cathode connects one 10-1000 ohm
Ohmic load 1, resistance and electrode extraction wire also need sealing waterproof and connect.Cathode zinc bar 7 is inserted into bottom sediment
In layer (ooze) 6, positive titanium carbon fiber brush frame 4 and ohmic load 1 are placed in seawater 3, obtain the combustion of sea-bottom deposit nitride layer zinc
Expect battery.The output voltage of the battery is that 1.0-1.3V(kirsite is different, and operating potential is different), electric current with load it is different without
Together.
Claims (5)
1. a kind of sea-bottom deposit nitride layer reactive metal fuel battery structure and device, it is characterised in that: using active metal as electricity
Pond negative electrode material is placed in sea-bottom deposit nitride layer, and using bottom sediment as electrolyte environment, conductive carbon material is placed in as anode
In sea water layer, using seawater as electrolyte environment, sea-bottom deposit nitride layer/sea water layer interface is realized as natural amberplex
Inside battery ionic conduction, positive and negative electrode is drawn by conducting wire respectively to be connected with instrument, constitutes cell circuit and open cell
Structure, battery cathode active metal provide electronics, and metal oxidation reaction occurs, and dissolved oxygen occurs for anode conductive carbon material also
Original reaction.
2. sea-bottom deposit nitride layer reactive metal fuel battery structure according to claim 1 and device, it is characterised in that: sea
Inside battery ionic conduction is realized as the natural amberplex of inside battery in bottom sediments nitride layer/seawater bed boundary.
3. sea-bottom deposit nitride layer reactive metal fuel battery structure according to claim 1 and device, it is characterised in that: electricity
Pond cathode is active metal magnesium, aluminium, zinc and its alloy.
4. sea-bottom deposit nitride layer reactive metal fuel battery structure according to claim 1 and device, it is characterised in that: electricity
Pond just extremely conductive carbon material.
5. sea-bottom deposit nitride layer reactive metal fuel battery structure according to claim 1 and device, it is characterised in that: electricity
Pond positive and negative anodes are connected with instrument load by external wire, are constituted cell circuit, used as structure opening formula power supply.
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海底生物燃料电池作为电源驱动小型电子器件的应用研究;付玉斌 等;《中国海洋大学学报》;20120731;第42卷;第93–98页 * |
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