CN105742634A - Metal matrix carbon fiber felt - Google Patents

Metal matrix carbon fiber felt Download PDF

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Publication number
CN105742634A
CN105742634A CN201410773068.3A CN201410773068A CN105742634A CN 105742634 A CN105742634 A CN 105742634A CN 201410773068 A CN201410773068 A CN 201410773068A CN 105742634 A CN105742634 A CN 105742634A
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CN
China
Prior art keywords
carbon fiber
metal
fiber felt
mesh
foam
Prior art date
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Pending
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CN201410773068.3A
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Chinese (zh)
Inventor
孙公权
王二东
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN201410773068.3A priority Critical patent/CN105742634A/en
Publication of CN105742634A publication Critical patent/CN105742634A/en
Pending legal-status Critical Current

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Abstract

The invention provides a metal matrix carbon fiber felt, which comprises a carbon fiber felt and a metal substrate, wherein the metal substrate is embedded into the carbon fiber felt; the metal substrate is a metal mesh or a foam metal; the fiber lengths of the metal matrix carbon fiber felt are 0.3-20mm; the thickness is 0.5-10mm; the conductivity of the metal matrix carbon fiber felt is 2-10S/cm; the metal substrate is one of a stainless steel mesh, a titanium mesh, a titanized mesh, a silver mesh, a silver-plated mesh, a gold mesh and a gold-plated mesh; the metal mesh number of a metal mesh structure is 10-1,000mesh; and the foam metal is one of nickel foam, copper foam and foam iron-nickel. Compared with the prior art, the metal matrix carbon fiber felt has the advantages that the carbon fibers grow inside the metal substrate and on the surface of the metal substrate; the contact resistance of the metal substrate and the carbon fibers is reduced; the strength of a single carbon fiber felt is improved; and the metal matrix carbon fiber felt has the advantages of high specific surface area of a cathode, good conductivity, high structural strength and the like when used as a dissolved oxygen seawater/salt water battery cathode, so that the performance and the stability of the battery are improved.

Description

A kind of metal-based carbon fiber felt
Technical field
The present invention relates to a kind of metal-based carbon fiber felt composite material, more particularly to a kind of for the metal-based carbon fiber felt of oxygen dissolving type cell cathode in sea water/saline.
Background technology
At sea or the electronic equipment worked in other saliferous waters, energy is provided as sea marker, Hydrometeorology, underwater detectoscope, wireless sensor etc. are required for adopting battery to be used as power supply.The requirement of battery is that capacity is big, stability is high by above-mentioned electrical equipment.Conventional one-shot battery, such as zinc-manganese, zinc-silver etc., price is high and quality and energy density per unit volume are low, and storge quality is poor.If with secondary cells such as plumbic acid, ni-mh, lithium ions, on the one hand, limited by its rated capacity, battery use limited time under water continuously;On the other hand, when working at deep-sea, cell sealing need to be protected in pressure vessel, especially lithium ion battery, add the complexity of system.
Oxygen dissolving type seawater battery is a kind of for battery under water, and its anode is magnesium, aluminum metal or alloy, and negative electrode is oxygen, and electrolyte is sea water or saline.Having the advantages of of such battery: one, energy density is high.Owing to this kind of battery its oxidant and electrolyte except metal anode provide by sea water, therefore its Theoretical Mass specific energy is up to hundreds of watt-hours every kilogram.Two, abundant raw material source.Magnesium, aluminum are the metallic element that earth reserves are big, and cheap.Three, storge quality is good.Such battery is in not state of activation when not contacting sea water, and its storge quality is good, stores for up to the several years.But, owing to oxygen dissolving type seawater battery utilizes oxygen in water as oxidant, and low (the only 0.3mol/m of oxygen content in sea water3), therefore negative electrode must adopt Open architecture and contact with sea water.Oxygen dissolving type seawater battery output larger current is made by increasing cathode area.
In order to expand seawater battery positive pole area in patent CN1543001A, adopting the structure of divergence expression positive pole, battery center is magnesium rod.The seawater battery magnesium anode of this structure with cathode distance farther out, adds ionic conductance, and cathode material specific surface area is relatively low, make battery performance on the low side.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is proposed to a kind of metal-based carbon fiber felt composite material, this material is with metallic substrates for currect collecting net, and the carbon fiber felt that internal in metallic substrates with growth in situ and surface carbon fiber is interwoven is for cathode composite.For achieving the above object, the present invention realizes by the following technical solutions.
A kind of metal-based carbon fiber felt, the carbon fiber of and outer surface internal in the hole of metallic substrates including metallic substrates with holes and growth in situ, the carbon fiber felt being interweaved between carbon fiber.
Described metallic substrates is wire netting or foam metal.
In described metal-based carbon fiber felt, carbon fiber length is 0.3mm-20mm;The thickness of described metal substrate surface carbon fiber felt is 0.5mm-10mm.
The electrical conductivity of described metal-based carbon fiber felt is 2-10S/cm.
Described wire netting is the one in stainless (steel) wire, titanium net, titanizing net, silver net, silver-plated net, gold net, gold-plated net.
Described foam metal is the one in nickel foam, foam copper, foam iron-nickel.
The order number of described wire netting is 1-100 order.
The porosity of described foam metal is 30%-98%.
Compared with prior art, metal-based carbon fiber felt of the present invention, its carbon fiber growth in situ is internal and surface in metallic substrates, reduce the contact resistance of metallic substrates and carbon fiber, add the intensity of single carbon fiber felt, it can be used as and there is during oxygen dissolving type sea water/salt battery negative electrode the advantages such as negative electrode specific surface area height, good conductivity, structural strength be big, thus improve performance and the stability of battery.
Accompanying drawing explanation
Fig. 1 is carbon felt type seawater battery cathode construction schematic diagram;
Fig. 2 is the Magnesium sea water battery discharge performance adopting carbon felt type negative electrode;
Fig. 3 discharge performance test figure.
In figure, 1 is carbon fiber felt;2 is collector.
Detailed description of the invention
Following embodiment is realize the possible approaches of the present invention, but the technical staff of same domain adopt the method beyond following manner come realize the present invention still this patent protection scope in.
Embodiment 1:
Following steps are adopted to prepare metal-based carbon fiber felt of the present invention.
To adopt order number be the titanium net of 20 orders is metallic substrates, by polypropylene cyanogen fiber shuttle-woven in titanium online metal-based carbon fiber felt precursor;By gained precursor in air atmosphere at 280 DEG C pre-oxidation 60min, then formed at 1000 DEG C of carbonization treatment 60min of nitrogen protection condition and namely form titanio carbon fiber felts.
Carbon fiber length in gained titanio carbon fiber felt is 15mm, and the integral thickness of titanio carbon fiber felt is 5mm, and its electrical conductivity is 8S/cm.Performance during for investigating it as oxygen dissolving type sea water/salt battery negative electrode, is cut into the laminated structure of 50cm × 18cm, and is sealed in its cut edge in Insulating frame and constitutes oxygen dissolving type seawater battery negative electrode.Oxygen dissolving type seawater battery includes 40 above-mentioned negative electrodes altogether.
Oxygen dissolving type sea water/salt battery anode adopts AZ61 magnesium alloy materials, and the oxygen dissolving type seawater battery of assembling discharge performance in the seawater is as shown in Figure 2.
Embodiment 2:
Polyacrylonitrile polymer is dissolved in the mixed solvent of dimethyl sulfoxide and water; continuously stirred 8h under 60 DEG C of conditions; obtain uniform polyacrylonitrile solution; nickel foam is placed in the device filling above-mentioned solution; vacuum defoamation 12h under 50 DEG C of conditions; have solution solvent evaporated after the deaeration of nickel foam by immersing, and in air atmosphere pre-oxidation 100min at 280 DEG C, then formed at 1000 DEG C of carbonization treatment 60min of nitrogen protection condition and namely form nickel foam base carbon fibre felts.
Embodiment 3:
Being dissolved in dimethylformamide by polyacrylonitrile polymer, under 60 DEG C of conditions, continuously stirred 2h is to being completely dissolved.The method adopting electrostatic spinning is online in gold plated copper by carrying out spinning after the fine spinning liquid inhalation syringe of polypropylene that mass fraction is 6%.Electrospinning fibre felt is placed in baking oven, at 280 DEG C of pre-oxidation 30min, is then formed at 1000 DEG C of carbonization treatment 60min of nitrogen protection condition and namely form gold-plated copper mesh base carbon fibre felt.
Comparative example:
Adopting titanium net in the same manner as in Example 1 as metallic substrates, in metallic substrates both sides pressing carbon fiber felt, form " three-in-one " structure, the integral thickness of " three-in-one " structure of formation is in the same manner as in Example 1.Adopting method in the same manner as in Example 1 that its conductivity metal is tested, test result shows that its electrical conductivity is 2.1S/cm, lower than the electrical conductivity test result in embodiment 1." three-in-one " is cut into size in the same manner as in Example 1, it can be used as oxygen dissolving type seawater battery negative electrode, anode and battery structure are all in the same manner as in Example 1 to be assembled into battery and it carries out discharge performance test in the seawater, and test result is as shown in Figure 3.Comparative example 1 it can be seen that because contact resistance is big, adopts the oxygen dissolving type seawater battery performance of " three-in-one " structure cathode to be significantly less than in embodiment 1 metal-based carbon fiber felt cathode cell performance of the present invention.Metal-based carbon fiber felt negative electrode of the present invention has good electrical conductivity, and battery performance is good and stable.

Claims (8)

1. a metal-based carbon fiber felt, it is characterised in that: include metallic substrates with holes and growth in situ in the carbon fiber of inside, the hole of metallic substrates and outer surface, the carbon fiber felt being interweaved between carbon fiber.
2. metal-based carbon fiber felt as claimed in claim 1, it is characterised in that: described metallic substrates is wire netting or foam metal.
3. metal-based carbon fiber felt as claimed in claim 1, it is characterised in that: in described metal-based carbon fiber felt, carbon fiber length is 0.3mm-20mm;The thickness of described metal substrate surface carbon fiber felt is 0.5mm-10mm.
4. metal-based carbon fiber felt as claimed in claim 1, it is characterised in that: the electrical conductivity of described metal-based carbon fiber felt is 2-10S/cm.
5. metal-based carbon fiber felt as claimed in claim 2, it is characterised in that: described wire netting is the one in stainless (steel) wire, titanium net, titanizing net, silver net, silver-plated net, gold net, gold-plated net.
6. metal-based carbon fiber felt as claimed in claim 2, it is characterised in that: described foam metal is the one in nickel foam, foam copper, foam iron-nickel.
7. metal-based carbon fiber felt as claimed in claim 2, it is characterised in that: the order number of described wire netting is 1-100 order.
8. metal-based carbon fiber felt as claimed in claim 2, it is characterised in that: the porosity of described foam metal is 30%-98%.
CN201410773068.3A 2014-12-12 2014-12-12 Metal matrix carbon fiber felt Pending CN105742634A (en)

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CN106654163A (en) * 2016-12-29 2017-05-10 中国电子科技集团公司第十八研究所 Preparation method for seawater dissolved oxygen battery cathode
CN109411764A (en) * 2018-10-30 2019-03-01 东南大学 A kind of preparation method of the compound lithium an- ode collector of nickel oxide-nickel foam
CN111278177A (en) * 2019-12-13 2020-06-12 中航复材(北京)科技有限公司 Preparation method of carbon material electric heating sheet

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN106654163A (en) * 2016-12-29 2017-05-10 中国电子科技集团公司第十八研究所 Preparation method for seawater dissolved oxygen battery cathode
CN109411764A (en) * 2018-10-30 2019-03-01 东南大学 A kind of preparation method of the compound lithium an- ode collector of nickel oxide-nickel foam
CN109411764B (en) * 2018-10-30 2021-06-11 东南大学 Preparation method of nickel nitride-nickel foam composite lithium metal negative current collector
CN111278177A (en) * 2019-12-13 2020-06-12 中航复材(北京)科技有限公司 Preparation method of carbon material electric heating sheet

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