CN102637890A - Lithium metal flow battery system and preparation method for same - Google Patents
Lithium metal flow battery system and preparation method for same Download PDFInfo
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- CN102637890A CN102637890A CN2012100886973A CN201210088697A CN102637890A CN 102637890 A CN102637890 A CN 102637890A CN 2012100886973 A CN2012100886973 A CN 2012100886973A CN 201210088697 A CN201210088697 A CN 201210088697A CN 102637890 A CN102637890 A CN 102637890A
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Abstract
A lithium metal flow battery system and a preparation method for the same belong to the field of electrochemical power sources. A cathode of a lithium metal flow battery is made of slurry formed by mixing lithium metal powder or lithium alloyed powder with organic liquid electrolyte containing lithium salt, an anode of the lithium metal flow battery is made of mixed slurry formed by the same organic liquid electrolyte and carbon catalyst or carbon-loaded catalyst, high-purity oxygen saturated in the slurry serves as oxidizer, a polymer composite membrane for separating the anode from the cathode is arranged in the middle, a lithium ion migrates between the two electrodes by means of the organic liquid electrolyte and the membrane, and an electron flows on an external lead connected with the anode and the cathode and a load to generate current. The novel lithium metal flow battery can be continuously used only by means of circulating feeding, and lithium metal can be regenerated by recovering discharge products in anode slurry and reused as cathode materials. The lithium metal flow battery system has the advantages of high energy density, continuous and stable operation, simple structure, long cycle life, high safety, high power density, and capability of realizing quick charge and discharge.
Description
Technical field
The present invention relates to utilize electrochemical reaction to carry out the field of chemical power source that electric energy transforms, be meant lithium metal liquid stream battery system and preparation method thereof especially.
Background technology
Along with society and rapid development of economy, energy shortage and problem of environmental pollution increasingly sharpen, and new forms of energy and the comprehensive exploitation of power conversion and storage system efficiently are the key subject of current social sustainable development with utilizing.Recent two decades comes, and is the development that the lithium ion battery on basis has been dominated heavy-duty battery with the lithium metal, and this is because lithium metal has low oxidation-reduction potential, low density and high electrochemical equivalent.Since Sony in 1991 is with the lithium ion battery industrialization, actively developed raising lithium ion battery energy density and electrode material Study on Stability so far in the global range, lithium ion battery is by extensively in fields of society.Though the electrochemistry capacitance of lithium metal is up to 3860mAhg
-1, but the electrochemistry capacitance of most of positive electrode has only 200mAhg
-1About, this has limited to the discharge capability of lithium ion battery, and the diffusion coefficient of lithium ion in the metal positive-pole material is generally 10 in addition
-8To 10
-11Cm
2s
-1About, this has also limited the energy output of lithium ion battery, thereby the raising space of the specific energy of the lithium ion battery that uses at present is limited, so must seek new battery system as its substitute.Metal-air cell provides high electrochemical performance, because in metal-air cell, is not stored in the battery from airborne active material oxygen, and wherein the theoretical energy density of lithium-air battery can reach 11140Whkg
-1, be that energy density is the highest in all metal pneumoelectric pond, be higher than conventional lithium-ion battery system far away, therefore enjoy attracting attention of domestic and international researcher.
Yet; Lithium-air battery actual capacity far below theoretical capacity; Still have many problems to wait to solve, the principal element that restricts its development and application at present has the following aspects: the discharging product (lithium oxide or lithium peroxide) that anodal oxygen reduction reaction generates is insoluble in liquid organic electrolyte, can be deposited in the microchannel of porous air electrode; Along with the carrying out of reaction blocked the passage that oxygen transmits gradually; Hindered oxygen diffusion to catalyst surface and with electrolyte in the contacting and reaction of lithium ion, guiding discharge stops, and influences its actual capacity and uses with continuing; Because lithium-air battery is in open environment, to work, there is the problem of volatilization easily in liquid organic electrolyte commonly used in addition, thereby has influenced the fail safe of discharge capacity, useful life and the battery of battery; The dendrite that the metal lithium sheet electrode generates in the charge and discharge cycles process is prone to cause short circuit after the diaphragm, and the replacing of metal lithium sheet also is a stubborn problem behind the long-play.Above-mentioned these problems have restricted the practical development and the application of lithium-air battery, and therefore developing the novel battery with high-performance and continuous service is chemical power source development key and focus.
Summary of the invention
The objective of the invention is to propose a kind of high-energy-density, continual and steady operation, simple in structure, high security, can " fill " the lithium metal liquid stream battery system that discharges fast.
The present invention also aims to the structure and the preparation method of lithium metal liquid stream battery system.
The lithium metal liquid stream battery system that the present invention also aims to propose; Can overcome lithium-air battery in the process of operation continuously; Because discharging product lithium oxide or the gradually deposition of lithium peroxide on porous air electrode microchannel are transmitted the problem that the duct guiding discharge stops thereby block oxygen.
The lithium metal liquid stream battery system that the present invention also aims to provide can overcome lithium-air battery in open environment continuously in the process of operation, and liquid organic electrolyte is volatile, battery capacity reduces, shorten and the low problem of fail safe useful life.
The lithium metal liquid stream battery system that the present invention also aims to provide can overcome lithium-air battery behind long-play, the problem that Li dendrite and metal lithium sheet are changed.
The present invention proposes the notion of lithium metal liquid stream battery system first, and battery structure and preparation method, and has proved its feasibility.
The lithium metal liquid stream battery system that the present invention proposes is made up of cell body and slurry delivery system; Cell body is made up of negative end plate 11, gasket seal 10, negative current collector groove 8, negative pole mixed slurry 1, polymer composite diaphragm 6, gasket seal 7, anodal mixed slurry 2, plus plate current-collecting body groove 9, positive end plate 12, and slurry delivery system is made up of slurry feed tube 3, slurry circulating pump 4, slurry storage tank 5.
Positive and negative electrode end plate of the present invention is processed by the high mechanical properties plate, comprises steel plate or aluminium alloy plate, but is not limited thereto, and this end plate plays the effect of being fixed and clamped; Positive and negative electrode collector groove is processed by the material of high electronic conductivity; Comprise graphite cake, corrosion resistant plate, but be not limited thereto, be respectively arranged with slurry above and import and export; The passage of positive and negative electrode slurry inflow and outflow is provided; The built-in circuitous water conservancy diversion groove of collector make slurry in order through and reaction, improve the utilance of electrode material, the effect of the playing collected current simultaneously again positive and negative electrode lead-out wire disjunctor part of holding concurrently.
Negative pole mixed slurry of the present invention is mixed with the organic solvent that contains lithium salts by metallic lithium powder or lithium alloy powder, and the concentration of metallic lithium powder or lithium alloy powder is 10molL
-1, but be not limited thereto concentration, can adjust its concentration according to the actual requirements, and the lithium alloy powder can be but be not limited to it and the alloy of silicon, germanium, tin.Described lithium salts can be LiPF
6, LiPF
4, LiClO
4, LiAsF
6, LiCF
3SO
3, LiN (CFSO
2)
2, LiC (SO
2CF
3)
3Wherein one or more of LiBOB; Organic solvent can be EC, PC, DMC, DEC, EMC, DME, 1; 3-dioxolanes, chain diethylene glycol dimethyl ether with and one or more combination such as homologue, above-mentioned lithium salts is dissolved in this organic solvent and is mixed with the liquid organic electrolyte that contains lithium salts.
Anodal mixed slurry of the present invention is mixed with the liquid organic electrolyte that contains lithium salts by the catalyst of material with carbon element catalyst or carbon load and is made by high purity oxygen gas is saturated, and catalyst concentration is 5molL in the anode sizing agent of being prepared
-1, but be not limited thereto concentration, can adjust its concentration according to the actual requirements.The catalyst of wherein said load can be metal simple-substance such as Pt with electrochemical catalysis hydrogen reduction, Pd, Au, Ag, Ru, Rh, Ir, Os, Co, Ni, Mo etc. and alloy thereof; Also comprise metal oxide such as α-MnO
2, β-MnO
2, γ-MnO
2, Mn
2O
3, Co
3O
4, CoO, WO
3, MoO
2, NiO, RuO
2Deng or its combination; Also comprise metal selenide such as manganese selenide, cobaltous selenide, cobaltous selenide, nickelous selenide, ferrous selenide, selenizing nail etc. or its combination; Also comprise metal nitride such as nitrogenized manganese, cobalt nitride, molybdenum nitride, nickel oxide, nitrided iron, nitrogenize ruthenium etc. or its combination; Also can be composite oxide of metal such as spinel-type, pyrochlore-type, Ca-Ti ore type etc.; Also comprise transition metal macrocyclic compounds such as phthalocyanine cobalt, ferriporphyrin; Above-mentioned one or several combination loads of these catalyst make the catalyst of carbon load, but are not limited thereto in carbon material surface, and wherein the mass content of catalyst is between 5% to 10%; Among the present invention in order to obtain well behaved carbon supported catalyst; And it is good with the liquid organic electrolyte compatibility; Selection have that synthesis technique is simple, cost is low, catalyst granules is uniformly dispersed and pattern is controlled mode prepare; Comprise immersion deposition method, colloid method, microemulsion method, vapour deposition process, microwave irradiation, spray pyrolysis etc., but be not limited to these methods.Said material with carbon element catalyst can be that powder granules such as active carbon, foamy carbon, graphite powder, carbonaceous mesophase spherules, CNT, carbon fiber, fullerene, Graphene and their oxygen or nitrogen mix up one or several combinations in the compound.
Polymer composite diaphragm involved in the present invention is by macromolecular material and inorganic material is compound makes; Wherein macromolecular material is including, but not limited to polypropylene, polyethylene, polyimides, PAEK, polynorbornene, polytetrafluoroethylene and composite material thereof, and inorganic material is including, but not limited to glass fiber, glass, silica, aluminium oxide, titanium oxide, magnesia, lithium metaaluminate, lithium titanate and composite material thereof; Said gasket seal is processed by silica gel sheet, teflon plate or PVC sheet, but is not limited thereto; The anode and cathode slurry feed tube is processed by stainless steel tube, silicone tube, teflon tube, but is not limited thereto; The positive and negative electrode slurry storage tank is processed by stainless steel, polytetrafluoroethylmaterial material, is used for storing respectively the positive and negative electrode slurry for preparing; Positive and negative electrode slurry circulating pump can use common business cycle pump or special circulating pump, when demonstrating with research work, can use peristaltic pump to replace circulating pump.
Beneficial effect of the present invention shows as; The lithium metal liquid stream battery system that is proposed adopts the lasting feed mode of airtight and independent turnover positive and negative electrode slurry; When being able to guarantee, security performance prevents to contain the volatilization of the liquid organic electrolyte of lithium salts; Improved the capacity of battery, and lithium metal is effectively protected, makes lithium/oxygen reaction only undertaken by electrochemical reaction; The holding vessel of positive and negative electrode slurry is mutually independently; Can realize that the moment of energy is additional through changing slurry; Make that battery can continuous service, and can improve the accumulation problem on electrode of anodal product, the useful life of having improved battery through circular treatment; And adopt metallic lithium powder or lithium alloy powder slurry to substitute and directly use the lithium sheet; Avoided thorny lithium sheet to change and the Li dendrite problem; Lithium powder or lithium alloy powder have higher discharge specific area than the lithium plate electrode simultaneously; Can significantly improve the lithium electrode situation under the heavy-current discharge condition, thereby make this battery have higher chemical property.
Description of drawings
Fig. 1 is the structural representation of lithium metal liquid stream battery system;
Fig. 2 is the cell body decomposition texture and assembling sketch map of lithium metal liquid stream battery system;
Fig. 3 is the collector sketch map of lithium metal liquid stream cell body;
Fig. 4 is the discharge curve of embodiment one lithium metal liquid stream battery;
Fig. 5 is the discharge curve of embodiment two lithium metal liquid stream batteries;
Fig. 6 is the discharge curve of embodiment three lithium metal liquid stream batteries;
Fig. 7 is the discharge curve of embodiment four lithium metal liquid stream batteries.
Embodiment
Below in conjunction with accompanying drawing, the present invention is lifted embodiment be elaborated.A lithium metal liquid stream battery system provided by the invention is as shown in Figure 1; Form by cell body and slurry delivery system; Cell body is made up of negative end plate 11, gasket seal 10, negative current collector groove 8, negative pole mixed slurry 1, polymer composite diaphragm 6, gasket seal 7, anodal mixed slurry 2, plus plate current-collecting body groove 9, positive end plate 12, and slurry delivery system is made up of slurry feed tube 3, slurry circulating pump 4, slurry storage tank 5.Said positive and negative electrode end plate is processed into by high mechanical properties steel plate or aluminium alloy plate, on four angles of end plate a hole is set respectively, is used for four screw self-contained batteries.Positive and negative electrode collector groove is processed by the graphite cake or the corrosion resistant plate of high electronic conductivity; On the collector groove, be processed with circuitous runner, and be processed with the input and output material hole, be connected with slurry feed tube 3 at its runner end at the whole story; And be provided with lead-out wire disjunctor part, as shown in Figure 3.Described cell body is left-right symmetric and center symmetry; And it is adaptive mutually; The centre is the polymer composite diaphragm 6 that is used to isolate anode sizing agent 2 and cathode size 1, and gasket seal 7 is placed in the barrier film both sides, and the left and right sides is respectively plus plate current-collecting body groove 9, negative current collector groove 8, gasket seal 10, positive end plate 12 and negative end plate 11 successively; Sequential cascade assembling as shown in Figure 2 compresses, through the screw and the gasket seal self-contained battery body at four angles.Positive and negative electrode slurry feed tube is processed by stainless steel tube, silicone tube or teflon tube, but is not limited thereto material, and this feed tube can closely cooperate with the feed inlet and outlet on the collector groove; The positive and negative electrode slurry storage tank is processed by corrosion-resistant material; Like stainless steel, polytetrafluoroethylene etc., it is provided with feed inlet and outlet, closely is connected with the slurry feed tube; Holding vessel also is provided with sealable raw material filler, the positive and negative electrode slurry that is used to annotate and prepares; Positive and negative electrode slurry circulating pump can use common business cycle pump or special circulating pump; When demonstrating with research work; Can use peristaltic pump to replace circulating pump, and circulating pump closely is connected with holding vessel with the slurry conveyance conduit, this slurry delivery system and cell body closely are connected the complete loop of cooperation formation one; Circulating pump can be opened or close according to the actual requirements, different slurry transporting velocities can be adjusted after the unlatching.
Use above-mentioned lithium metal liquid stream battery system, and adopt different positive and negative electrode slurries and polymer composite diaphragm to carry out discharge test, following examples are only explained the present invention, do not limit the present invention.
Practical implementation instance one
Adopt corrosion resistant plate to be processed as the positive and negative electrode end plate, on four angles of end plate a hole is set respectively, be used for four fixed screws; Adopt graphite cake to be processed into the positive and negative electrode collector groove of built-in circuitous runner; Adopting the composite membrane of polypropylene screen and silicon dioxide is barrier film, thickness be the 0.5mm silica gel pad as sealing gasket, its length and width size cooperates with the collector groove; Order as shown in Figure 2 is assembled successively, screw through four angles and the gasket seal cell body that is fixed and clamped; Inner and outer diameter is respectively that the stainless steel tube of 2mm and 4mm is as positive and negative electrode slurry feed tube; The stainless cylinder of steel of volume 50mL is as the positive and negative electrode slurry storage tank; Closely be connected to form complete closed loop with circulating pump 4 and cell body each other through stainless steel tube again, as shown in Figure 1; With metallic lithium powder and LiPF
6Concentration is 1molL
-1EC and DMC (volume ratio is 1: 1) liquid organic electrolyte mix, the concentration that is mixed with the lithium powder is 10molL
-1The negative pole mixed slurry; Prepare activated carbon loaded PdAu (being labeled as PdAu/C) as anode catalyst through immersion reduction method; Wherein the mass content of PdAu is 5% (Pd and Au atomic ratio are 1: 1); The liquid organic electrolyte of the same race that PdAu/C and above-mentioned negative pole use mixes, and the concentration that is mixed with PdAu/C is 5molL
-1Anodal utmost point mixed slurry; Inject the above-mentioned positive and negative electrode mixed slurry of preparing to the positive and negative electrode slurry storage tank of the above-mentioned lithium metal liquid stream battery system that assembles respectively; And in the anode sizing agent holding vessel, feed high purity oxygen with saturated anode sizing agent; Open two circulating pumps then; In the voltage range of 1.5V-3.5V, 0.1mA/cm
2Current density under carry out long-time discharge test, as shown in Figure 4 by this curve of 70 hours of battery discharge of implementing to be assembled, show higher discharge voltage between 2.65V to 2.75V.
Practical implementation instance two
As depicted in figs. 1 and 2, according to embodiment one said assembling lithium metal liquid stream battery system, positive and negative electrode slurry storage tank 5 closely is connected to form complete closed loop with circulating pump 4 and cell body through stainless steel tube 3 each other; With lithium silicon alloy powder (Li
44Si) and LiPF
6Concentration is 1molL
-1EC and DMC (volume ratio is 1: 1) liquid organic electrolyte mix, the concentration that is mixed with the lithium alloy powder is 10molL
-1The negative pole mixed slurry; The liquid organic electrolyte of the same race that active carbon and above-mentioned negative pole use mixes, and the concentration that is mixed with active carbon is 5molL
-1Anodal utmost point mixed slurry; Respectively to the above-mentioned lithium metal liquid stream battery system that assembles the positive and negative electrode slurry storage tank inject the above-mentioned positive and negative electrode mixed slurry of preparing; And in the anode sizing agent holding vessel, feed high purity oxygen with saturated anode sizing agent; Open two circulating pumps then; In the voltage range of 1.5V-3.5V, 0.1mA/cm
2Current density under carry out 50 hours discharge tests, the gained discharge curve is as shown in Figure 5, shows than stable discharge voltage (about 2.55V is to 2.65V).
Practical implementation instance three
With lithium powder and LiPF
6Concentration is 1molL
-1EC and DME (volume ratio is 1: 1) liquid organic electrolyte mix, the concentration that is mixed with the lithium powder is 10molL
-1The negative pole mixed slurry; Prepare activated carbon loaded PdAu (being labeled as PdAu/C) as anode catalyst through immersion reduction method; Wherein the mass content of PdAu is 5% (Pd and Au atomic ratio are 1: 1); The liquid organic electrolyte of the same race that PdAu/C and above-mentioned negative pole use mixes, and the concentration that is mixed with PdAu/C is 5molL
-1Anodal utmost point mixed slurry; According to embodiment one said assembling lithium metal liquid stream battery system, as depicted in figs. 1 and 2, positive and negative electrode slurry storage tank 5 closely is connected to form complete closed loop with circulating pump 4 and cell body through stainless steel tube 3 each other; Respectively to the above-mentioned lithium metal liquid stream battery system that assembles the positive and negative electrode slurry storage tank inject the above-mentioned positive and negative electrode mixed slurry of preparing; And in the anode sizing agent holding vessel, feed high purity oxygen with saturated anode sizing agent; Open two circulating pumps then; In the voltage range of 1.5V-3.5V, 0.1mA/cm
2Current density under carry out 23 hours discharge tests, the gained experimental result is as shown in Figure 6.
Practical implementation instance four
As depicted in figs. 1 and 2; According to embodiment one said assembling lithium metal liquid stream battery system; Barrier film adopts polyimide film and silicon dioxide composite membrane to replace aforementioned polypropylene screen and silicon dioxide composite membrane, and positive and negative electrode slurry storage tank 5 closely is connected to form complete closed loop with circulating pump 4 and cell body through stainless steel tube 3 each other; With lithium powder and LiPF
6Concentration is 1mol
L-1EC and DME (volume ratio is 1: 1) liquid organic electrolyte mix, the concentration that is mixed with the lithium powder is 10molL
-1The negative pole mixed slurry; Prepare activated carbon loaded PdAu (being labeled as PdAu/C) as anode catalyst through immersion reduction method; Wherein the mass content of PdAu is 5% (Pd and Au atomic ratio are 1: 1); The liquid organic electrolyte of the same race that PdAu/C and above-mentioned negative pole use mixes, and the concentration that is mixed with PdAu/C is 5molL
-1Anodal mixed slurry; Respectively to the above-mentioned lithium metal liquid stream battery system that assembles the positive and negative electrode slurry storage tank inject the above-mentioned positive and negative electrode mixed slurry of preparing; And in the anode sizing agent holding vessel, feed high purity oxygen with saturated anode sizing agent; Open two circulating pumps then; In the voltage range of 1.5V-3.5V, 0.1mA/cm
2Current density under carry out 16 hours discharge test, the gained discharge curve is as shown in Figure 7.
The operation principle of the lithium metal liquid stream battery system that the present invention relates to: the lithium in the cathode size discharges an electronics and generates lithium ion, after negative current collector and external circuit pass through load transfer to anodal, lithium ion passes barrier film through liquid organic electrolyte and arrives positive pole electronics simultaneously earlier; React at anodal lithium ion, electronics and oxygen atom; Generate lithium oxide or lithium peroxide, so just make externally circuit transmission and produce electric current of electronics, battery is through long-play; Lithium oxide or lithium peroxide are deposited on around the catalyst of carbon load gradually; And the lithium of negative pole also is consumed gradually, and inject fresh positive and negative electrode slurry through circulation this moment, can realize long circulation life; As long as guarantee the supply of positive and negative electrode slurry; Battery just can round-the-clock work, and make it regenerate lithium metal through the discharging product that reclaims in the anode sizing agent, can be used as negative material and recycle.
Claims (11)
1. lithium metal liquid stream battery system and preparation method thereof is characterized in that this battery system is made up of negative end plate (11), negative current collector groove (8), negative pole mixed slurry (1), gasket seal (7), polymer composite diaphragm (6), plus plate current-collecting body groove (9), anodal mixed slurry (2), gasket seal (10), positive end plate (12), slurry feed tube (3), slurry circulating pump (4), slurry storage tank (5); Sequential cascade assembling according to negative end plate (11), gasket seal (10), negative current collector groove (8), gasket seal (7), polymer composite diaphragm (6), gasket seal (7), plus plate current-collecting body groove (9), gasket seal (10), positive end plate (12) is fixed into cell body successively; The slurry feed tube closely is connected with the feed inlet and outlet of collector groove; And slurry conveyance conduit, slurry storage tank and circulating pump connect to form slurry delivery system; Behind the filling positive and negative electrode slurry, form inner sustainable conveying slurry and the outside lithium metal liquid stream battery system of power supply continuously in the holding vessel.
2. lithium metal liquid stream battery system according to claim 1; It is characterized in that all being provided with respectively above the positive and negative electrode collector groove positive and negative electrode slurry import and export; Be provided with circuitous water conservancy diversion groove in the collector groove; Make positive and negative electrode slurry one-dimensional order flow and reaction, the effect of the playing collected current simultaneously again positive and negative electrode lead-out wire disjunctor part of holding concurrently.
3. lithium metal liquid stream battery system according to claim 1 is characterized in that the positive and negative electrode collector groove that useful polymer composite diaphragm is isolated in the cell body, correspondingly flows through the positive and negative electrode slurry respectively and can not mix.
4. lithium metal liquid stream battery system according to claim 1 is characterized in that cell body is left-right symmetric and center symmetry, and adaptive mutually, stacks gradually assembling and compresses, and screw and gasket seal through four angles are fixed.
5. lithium metal liquid stream battery system according to claim 1; It is characterized in that said negative pole mixed slurry is to be mixed and made into by metallic lithium powder or lithium alloy powder and the liquid organic electrolyte that contains lithium salts, and the lithium alloy powder can be but be not limited to it and the alloy of silicon, germanium, tin.
6. lithium metal liquid stream battery system according to claim 1 is characterized in that said anodal utmost point mixed slurry is that catalyst by material with carbon element catalyst or carbon load mixes with the liquid organic electrolyte that contains lithium salts and made by high purity oxygen gas is saturated.
7. be that powder granules such as active carbon, foamy carbon, graphite powder, carbonaceous mesophase spherules, CNT, carbon fiber, fullerene, Graphene and their oxygen or nitrogen mix up one or several combinations in the compound according to the said material with carbon element catalyst of claim 6.
8. be metal simple-substance such as Pt with electrochemical catalysis hydrogen reduction, Pd, Au, Ag, Ru, Rh, Ir, Os, Co, Ni, Mo etc. and alloy thereof according to the catalyst of the said load of claim 6; Also comprise metal oxide such as α-MnO
2, β-MnO
2, γ-MnO
2, Mn
2O
3, Co
3O
4, CoO, WO
3, MoO
2, NiO, RuO
2Deng or its combination; Also comprise metal selenide such as manganese selenide, cobaltous selenide, cobaltous selenide, nickelous selenide, ferrous selenide, selenizing ruthenium etc. or its combination; Also comprise metal nitride such as nitrogenized manganese, cobalt nitride, molybdenum nitride, nickel oxide, nitrided iron, nitrogenize ruthenium etc. or its combination; Also can be composite oxide of metal such as spinel-type, pyrochlore-type, Ca-Ti ore type etc.; Also comprise transition metal macrocyclic compounds such as phthalocyanine cobalt, ferriporphyrin; And the combination of above-mentioned these nanocatalysts.
9. the catalyst according to the said carbon load of claim 6 is to choose the one or more combination of the said material with carbon element of claim 7 as carrier; Through immersion deposition method, colloid method, microemulsion method, vapour deposition process, microwave irradiation, spray pyrolysis etc.; One or more combination at the said catalyst of its surface in situ load claim 8; Make the catalyst of carbon load, wherein the mass content of catalyst is between 5% to 10%.
According to the said polymer composite diaphragm macromolecular material of claim 1 including, but not limited to polypropylene, polyethylene, polyimides, PAEK, polynorbornene, polytetrafluoroethylene and composite material thereof, inorganic material is including, but not limited to glass fiber, glass, silica, aluminium oxide, titanium oxide, magnesia, lithium metaaluminate, lithium titanate and composite material thereof.
11. can be LiPF according to claim 5 with 6 said used lithium salts
6, LiPF
4, LiClO
4, LiAsF
6, LiCF
3SO
3, LiN (CFSO
2)
2, LiC (SO
2CF
3)
3Wherein one or more of LiBOB; Organic solvent can be EC, PC, DMC, DEC, EMC, DME, 1,3-dioxolanes, chain diethylene glycol dimethyl ether with and one or more combination such as homologue, lithium salts is dissolved in this organic solvent and is mixed with the liquid organic electrolyte that contains lithium salts.
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