CN103746146A - Cathode module and lithium battery applying same - Google Patents
Cathode module and lithium battery applying same Download PDFInfo
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- CN103746146A CN103746146A CN201310461122.6A CN201310461122A CN103746146A CN 103746146 A CN103746146 A CN 103746146A CN 201310461122 A CN201310461122 A CN 201310461122A CN 103746146 A CN103746146 A CN 103746146A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A cathode module can be applied in a lithium battery and comprises a cathode sheet, a first separating film, a second separating film soaked with an organic electrolyte or a polymer electrolyte. An independent space is formed by the first separating film; the second separating film soaked with the organic electrolyte or the polymer electrolyte is filled in the independent space formed by the first separating film; the cathode sheet is wrapped in the second separating film soaked with the organic electrolyte or the polymer electrolyte, and is in interval arrangement with the first separating film. The lithium battery comprises an anode, a water electrolyte and the cathode module; the cathode mode and the anode are in interval arrangement, and the water electrolyte is at least arranged between the cathode module and the anode.
Description
Technical field
The present invention relates to a kind of negative pole module and apply the lithium battery of this negative pole module, relate in particular to a kind of this negative pole module of application organic-water two-electrolyte lithium battery.
Background technology
With each state of the west headed by the U.S., all the hope of alleviating energy crisis and ambient pressure is placed in the development of New Energy Industry, the development of New Energy Industry has been carried out to policy inclination and the support of great dynamics.The focus of New Energy Industry present stage is the energy storage system of large-scale energy-accumulating power station and pure electric automobile.These two energy storage systems are all to be combined by connection in series-parallel by a large amount of cells, have huge feature.Since huge, very harsh to the fail safe of battery and conforming requirement.
Lithium battery in the past two more than ten years have technically huge development, with respect to battery systems such as plumbic acid, NI-G, ni-mhs, the advantage that lithium battery has that specific energy is high, voltage is high and the life-span is long.But lithium battery generally adopts organic substance to do electrolyte in prior art, because organic substance flash-point is lower, poor stability, easily decomposes and blast on fire, so lithium battery fail safe is poor.In addition, the ionic conductance of organic bath is low, power-performance and energy density to shortcoming not only can the limit lithium battery such as the wettability of inorganic active material is poor, also can cause the poor problem of cell consistency.Prior art is by combining to obtain high capacity cell by the connection in series-parallel of dozens of lithium battery, if the difference between series-parallel a plurality of cell is excessive, be easy to cause battery that capacity is little to overcharge and cross and put phenomenon, cause this cell to damage too early, thereby affect the life-span of whole Battery pack.J.R.Dahn has proposed the concept of water system electrolyte lithium battery in 1994, although use water system electrolyte can solve a lot of difficult problems of using organic bath to bring, but the use voltage of water system electrolyte lithium battery must be lower than the decomposition voltage of water, this has significantly reduced again the energy density of battery.
Summary of the invention
In view of this, necessaryly provide that a kind of fail safe is good, energy density is high, power-performance good, can under large multiplying power, discharge and recharge, operating voltage is high and the lithium battery of high conformity.
The invention provides a kind of negative pole module, can be applicable to lithium battery, comprise: a negative plate, one organic bath and one first barrier film, described the first barrier film formation one is space independently, described organic bath is filled in described first in film formed independently space, and described negative plate is immersed in described organic bath, and arranges with described the first barrier film interval.
Described negative pole module further comprises that one second barrier film is wrapped in described negative plate surface.
The invention provides a kind of lithium battery, comprising: negative pole module described in a positive pole, a water system electrolyte and, described negative pole module and described anodal interval arrange, and described water system electrolyte is at least arranged between described negative pole module and described positive pole.
Compared with prior art, lithium battery of the present invention is assembled into negative pole module by negative pole and uses, organic-water two-electrolyte structure that this negative pole module not only can make lithium battery have, and can change to improve the anodal utilance of lithium battery, reduce the cost of lithium battery.The lithium battery with organic-water two-electrolyte can be taken into account excellent power-performance and high energy density, also has higher operating voltage simultaneously, can under large electric current, discharge and recharge.
Accompanying drawing explanation
The structural representation of the negative pole module that Fig. 1 provides for first embodiment of the invention.
The structural representation of the negative pole module that Fig. 2 provides for second embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 3 provides for third embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 4 provides for fourth embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 5 provides for fifth embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 6 provides for sixth embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 7 provides for seventh embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 8 provides for eighth embodiment of the invention.
The structural representation of the lithium ion battery that Fig. 9 provides for ninth embodiment of the invention.
The structural representation of the lithium-air battery that Figure 10 provides for tenth embodiment of the invention.
The structural representation of the lithium-air battery that Figure 11 provides for eleventh embodiment of the invention.
The structural representation of the lithium-air battery that Figure 12 provides for twelveth embodiment of the invention.
The structural representation of the lithium-air battery that Figure 13 provides for thriteenth embodiment of the invention.
The structural representation of the lithium-air battery that Figure 14 provides for fourteenth embodiment of the invention.
Figure 15 is the charging and discharging curve of example 1 lithium ion battery of the present invention.
Figure 16 is the cyclic curve of example 1 lithium ion battery of the present invention.
Main element symbol description
| |
100、200 |
| Anodal |
300、400、500、600 |
| |
10、20、30、40、50、60、70 |
| Lithium- |
80、82、84、86、88 |
| |
102 |
| Anodal | 202，302 |
| |
104 |
| |
204、214 |
| The |
106 |
| The second barrier film | 206 |
| |
306 |
| Outer enclosure structure | 220 |
Following embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments lithium ion battery provided by the invention and preparation method thereof is described in further detail.
Refer to Fig. 1, first embodiment of the invention provides a kind of negative pole module 100 that is applied to lithium battery, and this negative pole module 100 comprises negative plate 102, one organic baths 104 and one first barrier film 106.Described the first barrier film 106 formation one are space independently, and the shape in described space is not limit, and can design according to the actual requirements.Described organic bath 104 is filled in the space of whole the first barrier film 106 formation, and described negative plate 106 is immersed in described organic bath 104 completely.This negative pole module 100 is an independently integral body, detachable, replaceable.
Described negative plate 102 arranges to avoid this negative plate 102 to contact with this first barrier film 106 with described the first barrier film 106 intervals.This negative plate 102 and this first barrier film 106 intervals arrange and can make to form a potential difference between this negative plate 102 and this first barrier film 106, from lithium battery is used under higher operating voltage.
The composition that consists of negative plate conventional in lithium battery of described negative plate 102.Described negative plate 102 can comprise negative current collector and coating or be filled in the negative material of described negative current collector.Described negative material can comprise negative electrode active material, conductive agent and binding agent.Described negative electrode active material is for embedding and disengage the negative electrode active material of lithium.Preferably, described negative electrode active material can be one or more in graphite, material with carbon element and alloy material.Described conductive agent is conductive agent conventional in lithium battery, and for example described conductive agent can be one or more in graphite, acetylene black and carbon nano-tube.Described binding agent is binding agent conventional in lithium battery, and for example described binding agent can be one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).Described negative current collector is negative current collector conventional in lithium battery, and for example described negative current collector can be one or more of Copper Foil, nickel foil, titanium foil and aluminium foil.Described negative plate 102 also can directly adopt metal lithium sheet or lithium alloy.
The thickness of described negative plate 102 is unrestricted.Preferably, the thickness of described negative plate 102 is 5 to 10 times of negative plate thickness of the prior art lithium ion battery that adopts organic bath.More preferably, the thickness of described negative plate 102 is that 100 μ m are to 1000 μ m.The most preferably, the thickness of described negative plate 102 is that 200 μ m are to 800 μ m.In embodiments of the present invention, the thickness of described negative plate 102 is 400 μ m.
Described negative plate 102 also comprises a negative bus-bar (not shown), and described negative bus-bar is used for making negative plate 102 to be electrically connected to external circuit.
Described organic bath 104 can be one or more in organic electrolyte, organic colloid electrolyte and organic solid-state electrolyte.Described organic electrolyte is that lithium salts is dissolved in the solution that organic solvent forms.Described lithium salts is LiClO
4, LiBF
4, LiPF
6, LiBOB, LiODFB and LiTFSI one or more.Described organic solvent be second eyeball, tetrahydrochysene bark mutter, one or more in vinyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate or dimethyl alum.Described organic colloid electrolyte can be polymeric colloid electrolyte.Described organic solid electrolyte based can be copolymer solid electrolyte.
106, described the first barrier film allows lithium ion to pass through, and does not allow hydrone to pass through.Preferably, described the first barrier film 106 can have certain rigidity, and the barrier film with certain rigidity is easier to processing.More preferably, described the first barrier film 106 can be one or more in anodic aluminium oxide membrane and the composite diaphragm that contains hydrophobic amberplex.The most preferably, described barrier film can be inorganic porous hydrophobic rigid diaphragms.Described inorganic porous hydrophobic rigid diaphragms can be for crystalline state lithium ion solid electrolyte barrier film, glassy state lithium ion solid electrolyte barrier film and lithium ion be at lithium ion transmission films such as exchange Nafion films.Described crystalline state lithium ion solid electrolyte barrier film can be for having the lithium ion solid electrolyte barrier film of LISICON structure, NASICON structure or perovskite structure.Described glassy state lithium ion solid electrolyte barrier film can be oxide type, sulfide type or mixed type glassy state lithium ion solid electrolyte barrier film.Described lithium battery can be lithium ion battery, lithium metal battery or lithium-air battery.
Described negative pole module 100 can be directly and positive pole and water system electrolyte ingredient lithium battery use, lithium battery is had organic-water two-electrolyte structure, and this negative pole module 100 is detachable and replaceable, can reduce battery cost, can improve again the utilance of battery.
Described water system electrolyte can be liquid water system electrolyte or gel state water system electrolyte.
Refer to Fig. 2, second embodiment of the invention further provides a kind of negative pole module 200, this negative pole module 200 comprises a negative plate 102, an organic bath 104 and one first barrier film 106, in the structure of this negative pole module 200 and aforementioned the first embodiment, the structure of negative pole module 100 is basic identical, difference is, described negative pole module 200 further comprises that one second barrier film 206 is wrapped in described negative plate 102 surfaces, so that described negative plate 102 and the first barrier film 106 separate.This negative pole module 200 is followed successively by the first barrier film 106, organic bath 104, the second barrier film 206 and negative plate 102 from outside to inside.Adopt the second barrier film 206 to be wrapped in that described negative plate 102 surfaces can make negative plate 102 and first barrier film 106 is more effective separates, better guarantee the existence of potential difference between negative plate 102 and the first barrier film 106.When described organic bath 104 is organic colloid electrolyte or organic solid-state electrolyte, also can adopt the second barrier film and negative plate 102 is wrapped in described organic colloid electrolyte or described organic solid-state electrolyte so that negative plate 102 and first barrier film 106 is more effective separates.
Described the second barrier film 206 materials can adopt diaphragm material conventional in lithium battery.Particularly, described the second barrier film 206 is preferably the micro-nylon felt of composite membrane, modified polypropene felt, polyethylene felt, glass mat, ultra-fine fibre glass paper of polyalkene diaphragm, polyalkene diaphragm and one or more in nylon felt.
Refer to Fig. 3, third embodiment of the invention further provides a kind of lithium ion battery 10, this lithium ion battery 10 comprises negative pole module 100, anodal 202 and liquid water system electrolyte 204, described anodal 202 and described negative pole module 100 can be infiltrated in described liquid water system electrolyte 204.This negative pole module 100 is an independently integral body, detachable, replaceable.
Described lithium ion battery 10 can further comprise an outer enclosure structure (not shown).This outer enclosure structure can be by this positive pole 202, this liquid state water system electrolyte 204 and 100 encapsulation of this negative pole module therebetween.
Described anodal 202 arrange with described negative pole module 100 intervals, so that described anodal 202 do not contact with described negative pole module 100, thereby make described anodal 202, described the first barrier film 106 and the 102 spaces settings of described negative plate.Described anodal 202 and described the first barrier film 106 intervals arrange can described anodal 202 and described the first barrier film 106 between form first potential difference.Described the first barrier film 106 and described negative plate 102 intervals arrange and can between described the first barrier film 106 and described negative plate 102, form second potential difference, described anodal 202 and described negative plate 102 between potential difference be the first potential difference and the second potential difference and, thereby make this lithium ion battery 10 there is higher operating voltage.In embodiments of the present invention, described the first potential difference is 1 volt to 2 volts, described the second potential difference is 2.5 volts to 3.5 volts, and between described positive pole and described negative plate, potential difference is 3.5 volts to 5.5 volts, so the operating voltage of the lithium ion battery 10 of the embodiment of the present invention can be 3.5 volts to 5.5 volts.
Described anodal 202 consist of in lithium ion battery conventional anodal composition.Described anodal 202 can comprise plus plate current-collecting body and coating or be filled in the positive electrode of described plus plate current-collecting body.Described positive electrode can comprise positive active material, conductive agent and binding agent.Described positive active material is for embedding the positive active material with removal lithium embedded.Preferably, described positive active material can be one or more in the materials such as LiMn2O4, layered lithium manganate, lithium nickelate, cobalt acid lithium, LiFePO4, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide and the elemental sulfur of the spinel structure of doping or doping not, ferric flouride, copper fluoride.Described conductive agent is conductive agent conventional in lithium ion battery, and for example described conductive agent can be one or more in graphite, acetylene black and carbon nano-tube.Described binding agent is for being conventional binding agent in lithium ion battery, and for example described binding agent can be one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).Described plus plate current-collecting body is plus plate current-collecting body conventional in lithium ion battery, and for example described plus plate current-collecting body can be one or more of Copper Foil, nickel foil, titanium foil and aluminium foil.
Described anodal 202 also comprise a positive bus (not shown), and described positive bus is for making positive pole be electrically connected to outside circuit.
Described anodal 202 thickness is unrestricted.Preferably, described anodal 202 thickness is 3 to 30 times of anodal thickness of the prior art lithium ion battery that adopts organic bath.More preferably, described anodal 202 thickness is that 500 μ m are to 2000 μ m.The most preferably, described anodal 202 thickness is that 1000 μ m are to 2000 μ m.In embodiments of the present invention, described anodal 202 thickness is 1000 μ m.
Described liquid water system electrolyte 204 is Aqueous Lithium Salts.Described lithium salts can be one or more in inorganic lithium salt and organic lithium salt.Described inorganic lithium salt can be one or more of halide, sulfide, sulfate, nitrate and the carbonate of lithium metal.Described organic lithium salt can be one or more of carboxylate and sulfonate.
Refer to Fig. 4, fourth embodiment of the invention further provides a kind of lithium ion battery 20, this lithium ion battery 20 comprises negative pole module 100, positive pole 202 and liquid water system electrolyte 204, in the structure of this lithium ion battery 20 and aforementioned the 3rd embodiment, the structure of lithium ion battery 10 is basic identical, difference is, described lithium ion battery 20 further comprises an electrolyte carrier 30 as one kind 6, described liquid water system electrolyte 204 is adsorbed in this electrolyte carrier 30 as one kind 6, described anodal 202 and described negative pole module 100 be all arranged at this electrolyte carrier 30 as one kind 6 inside.
Described electrolyte carrier 30 as one kind 6 has certain thickness.Described electrolyte carrier 30 as one kind 6 can be porous material, and can be by described liquid water system electrolyte 204 absorption therebetween.Described electrolyte carrier 30 as one kind 6 can play fixation to described positive pole and described negative pole module, makes the use of described lithium ion battery 20 safer.Described electrolyte carrier 30 as one kind 6 can be one or more of glass fibre cotton and silicon gel.
Refer to Fig. 5, fifth embodiment of the invention further provides a kind of lithium ion battery 30, this lithium ion battery 30 comprises negative pole module 100, positive pole 202 and liquid water system electrolyte 204, described liquid water system electrolyte 204 is adsorbed in an electrolyte carrier 30 as one kind 6, in the structure of this lithium ion battery 30 and aforementioned the 4th embodiment, the structure of lithium ion battery 20 is basic identical, its difference is, only described anodal 202 be arranged at an inner independently whole anodal module 300, the described anodal module 300 and the stacked setting of described negative pole module 100 of forming of electrolyte carrier 30 as one kind 6.Described anodal module 300 is also detachable, replaceable.
Refer to Fig. 6, sixth embodiment of the invention further provides a kind of lithium ion battery 40, this lithium ion battery 40 comprises negative pole module 100, positive pole 202 and liquid water system electrolyte 204, described liquid water system electrolyte 204 is adsorbed in an electrolyte carrier 30 as one kind 6, in the structure of this lithium ion battery 40 and aforementioned the 4th embodiment, the structure of lithium ion battery 20 is basic identical, its difference is, described anodal 202 and stacked setting of described electrolyte carrier 30 as one kind 6 form an independently whole anodal module 400, described anodal module 400 and the stacked setting of described negative pole module 100, described electrolyte carrier 30 as one kind 6 be arranged at described anodal 202 and described negative pole module 100 between, described anodal 202 and described negative pole module 100 intervals arrange.Described anodal module 400 is also detachable, replaceable.
Refer to Fig. 7, seventh embodiment of the invention further provides a kind of lithium ion battery 50, this lithium ion battery 50 comprises negative pole module 100, positive pole 202 and gel state water system electrolyte 214, in the structure of this lithium ion battery 50 and aforementioned the 3rd embodiment, the structure of lithium ion battery 10 is basic identical, difference is, described anodal 202 and described negative pole module 100 be all infiltrated in described gel state water system electrolyte 214.Described gel state water system electrolyte 214 can be comprised of Aqueous Lithium Salts and hydrophilic polymer.
Refer to Fig. 8, eighth embodiment of the invention further provides a kind of lithium ion battery 60, this lithium ion battery 60 comprises negative pole module 100, positive pole 202 and gel state water system electrolyte 214, in the structure of this lithium ion battery 60 and aforementioned the 7th embodiment, the structure of lithium ion battery 50 is basic identical, difference is, only described anodal 202 is arranged at that described gel state water system electrolyte 214 is inner forms an independently whole anodal module 500.Described anodal module 500 and the stacked setting of described negative pole module 100.Described anodal module 500 is also detachable, replaceable.
Refer to Fig. 9, ninth embodiment of the invention further provides a kind of lithium ion battery 70, this lithium ion battery 70 comprises negative pole module 100, positive pole 202 and gel state water system electrolyte 214, in the structure of this lithium ion battery 70 and aforementioned the 7th embodiment, the structure of lithium ion battery 50 is basic identical, its difference is, described anodal 202 and stacked setting of described gel state water system electrolyte 214 form an independently whole anodal module 600, described anodal module 600 and the stacked setting of described negative pole module 100, described gel state water system electrolyte 214 be arranged at described anodal 202 and described negative pole module 100 between, described anodal 202 and described negative pole module 100 intervals arrange.Described anodal module 600 is also detachable, replaceable.
In addition, in above-mentioned the 3rd embodiment to the nine embodiment the described negative pole module 100 of arbitrary embodiment also the described negative pole module in replaceable one-tenth the second embodiment 200 form lithium ion batteries.
The present invention is by adopting the first barrier film to form independently space, negative pole and electrolyte is arranged on to first and in film formed space, is combined into independently negative pole module and uses, and makes described negative pole module detachable, replaceable.The normal operation that keeps lithium ion battery by the replacing of negative pole module, can reduce costs, and can improve again the utilance of material.Effectively overcome the negative material structural deterioration that in prior art, lithium ion battery causes due to the change in volume of negative material in removal lithium embedded process, and then cause negative plate distortion to cause lithium ion battery battery chemical cycle stability decreases, the technical problems such as the volume lowering of lithium ion battery.
In addition, the present invention is assembled into lithium ion battery by negative pole module, positive pole and water system electrolyte, the organic-water two-electrolyte structure that can make lithium ion battery have.The positive pole of lithium ion battery is used water system electrolyte, because the ionic conductance of water is than high two orders of magnitude of organic bath, and water is better to the wettability of active material, therefore compare with simple use organic bath, the internal resistance of lithium ion battery reduces greatly, not only can improve the high rate charge-discharge performance of lithium ion battery, also can make anodal unrestricted with the thickness of negative plate.
The thickness of positive/negative plate is unrestricted, conforming impact reduces on cell not only to make error in positive/negative plate coating process, improved the consistency of lithium ion battery, and can make the load capacity of the positive active material of positive/negative plate unit are greatly improve, thereby the energy density of lithium ion battery is greatly improved, and therefore lithium ion battery provided by the invention can be taken into account power-performance and energy density.
The lithium ion battery that the third embodiment of the invention of only take below provides is the preparation method of example explanation negative pole module and lithium ion battery, mainly comprises following step:
S1, provides plus plate current-collecting body, at this plus plate current-collecting body surface-coated positive electrode, forms anodal;
S2, provides negative current collector, at this negative current collector surface-coated negative material, forms negative plate;
S3, is coated with machine electrolyte at described negative plate;
S4, product prepared by step S3 is wrapped in the anodic aluminium oxide membrane of rigidity and sealing, forms negative pole module;
S5, puts into battery container negative pole module and positive pole, injects water system electrolyte sealing in battery container, obtains lithium ion battery.
In above-mentioned steps S1 and S2, can to described positive and negative electrode collector, film by film applicator.Particularly, first positive active material and negative electrode active material are mixed with conductive agent and binder solution respectively, form anode sizing agent and cathode size, then by film applicator, positive and negative electrode slurry is coated respectively to positive and negative electrode collection liquid surface dry, form positive and negative plate.Further, can to the positive and negative plate of coating, carry out compacting by film laminator.
Above-mentioned steps S3 can be further comprising the steps:
(1) at coated the second barrier film in negative plate surface;
(2) by described negative plate and described the second barrier film saturated adsorption organic electrolyte.
The preparation method of the lithium ion battery of other embodiment of the present invention can adjust based on the above method, does not repeat them here.
Refer to Figure 10, tenth embodiment of the invention further provides a kind of lithium-air battery 80, and this lithium-air battery 80 comprises negative pole module 100, positive pole 302 and liquid water system electrolyte 204.Described anodal 302 is air electrode, and described air electrode and described negative pole module 100 intervals arrange.Described negative pole module 100 is immersed in described water system electrolyte 204.
The air electrode conventional in lithium-air battery that consists of of described air electrode forms.Described air electrode 308 can comprise catalyst, catalyst carrier and binding agent.Described catalyst can make to be dissolved in the oxygen generation electrochemical reaction in water system electrolyte.Described catalyst can be one or more in single metal oxide, composite oxide of metal and metal simple-substance.Preferably, described catalyst is Pt nanoparticle, gold nano grain, plation nano particle, platinum cobalt alloy nano particle, platinum evanohm nano particle, platinum-nickel alloy nano particle, MnO
2one or more in nano particle, MoN nano particle, MnN nano particle and ternary metal nitride.Described catalyst carrier is catalyst carrier conventional in lithium-air battery.Described catalyst carrier can, for material with carbon elements such as Graphene, carbon nano-fiber, carbon nano-tube, hollow carbon sphere, ordered mesopore carbon, porous activated carbons, can be also the carriers such as polymer support, metallic organic framework or complex carrier.Described binding agent is binding agent conventional in lithium-air battery, and described binding agent can be one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).
Refer to Figure 11, eleventh embodiment of the invention further provides a kind of lithium-air battery 82, this lithium-air battery 82 comprises negative pole module 100, positive pole 302 and liquid water system electrolyte 204, in the structure of this lithium-air battery 82 and aforementioned the tenth embodiment, the structure of lithium-air battery 80 is basic identical, difference is, described lithium-air battery 82 further comprises an electrolyte carrier 30 as one kind 6, described liquid water system electrolyte 204 is adsorbed in this electrolyte carrier 30 as one kind 6, and described negative pole module 100 is arranged at this electrolyte carrier 30 as one kind 6 inside.
Refer to Figure 12, twelveth embodiment of the invention further provides a kind of lithium-air battery 84, this lithium-air battery 84 comprises negative pole module 100, positive pole 302 and liquid water system electrolyte 204, in the structure of this lithium-air battery 84 and aforementioned the tenth embodiment, the structure of lithium-air battery 80 is basic identical, difference is, described lithium-air battery 82 further comprises an electrolyte carrier 30 as one kind 6, described liquid water system electrolyte 204 is adsorbed in this electrolyte carrier 30 as one kind 6, described anodal 302, described negative pole module 100 and the stacked setting of described electrolyte carrier 30 as one kind 6, described electrolyte carrier 30 as one kind 6 be arranged at described anodal 302 and described negative pole module 100 between, described anodal 302 and described negative pole module 100 intervals arrange.
Refer to Figure 13, thriteenth embodiment of the invention further provides a kind of lithium-air battery 86, this lithium-air battery 86 comprises negative pole module 100, positive pole 302 and gel state water system electrolyte 214, in the structure of this lithium-air battery 86 and aforementioned the tenth embodiment, the structure of lithium-air battery 80 is basic identical, difference is, described negative pole module 100 is arranged at described gel state water system electrolyte 214 inside.
Refer to Figure 14, fourteenth embodiment of the invention further provides a kind of lithium-air battery 88, this lithium-air battery 88 comprises negative pole module 100, positive pole 302 and gel state water system electrolyte 214, in the structure of this lithium-air battery 88 and aforementioned the tenth embodiment, the structure of lithium-air battery 80 is basic identical, difference is, described anodal 302, described negative pole module 100 and described gel state water system electrolyte 214 stacked settings, described gel state water system electrolyte 214 be arranged at described anodal 302 and described negative pole module 100 between, described anodal 302 and described gel state water system electrolyte 214 intervals arrange.
In addition, in above-mentioned the tenth embodiment to the 14 embodiment the described negative pole module 100 of arbitrary embodiment also the described negative pole module in replaceable one-tenth the second embodiment 200 form lithium ion batteries.
Lithium-air battery be take lithium metal as negative pole, and oxygen is anodal, and in theory because oxygen is unrestricted as anode reactant, the capacity of lithium-air battery only depends on cathode of lithium.Lithium-air battery is in long-time discharge process, and the lithium metal of negative pole is along with the carrying out of electric discharge constantly consumes, and when the lithium metal of negative pole is exhausted, and air electrode can also normally be used.Negative pole module of the present invention is removable, and the normal operation that now can keep lithium-air battery by changing negative pole module, can reduce costs, and can improve again the utilance of air electrode.
Organic-water two-electrolyte structure that the present invention adopts negative pole module can make lithium-air battery have.Air electrode adopts water system electrolyte, can avoid adopting organic bath that discharging product lithia or lithium peroxide are separated out and be deposited on air electrode and the problem that the air loop causing stops up.The discharging product of air electrode in aqueous systems electrolyte is LiOH, has water-soluble characteristic, can not pile up at air electrode place, is conducive to carrying out smoothly of electric discharge.Cathode of lithium adopts organic bath, and described negative pole module can exclusion of water enter, and can avoid cathode of lithium and water to react and cause cathode of lithium corrosion.
Example 1.
1) positive electrode is 80% LiFePO4,10% polytetrafluoroethylene, 10% acetylene black mixing, stirs into uniform slurry, and slurry is coated in nickel foam and through compressing tablet becomes anode pole piece, and pole piece thickness is 600 microns;
2) the lithium sheet that cathode pole piece is 200 microns by thickness forms;
3) cathode pole piece coated outside polypropylene (PP) barrier film, PP barrier film and cathode pole piece all saturated adsorption by the organic bath that is dissolved in lithium hexafluoro phosphate that vinyl carbonate that mass ratio is 1:1 and the concentration in Methylethyl carbonic ester mixed solvent are 1mol/l and prepares;
4) 3) prepare in the anodic aluminium oxide membrane that product is wrapped in rigidity and sealing to obtain negative pole module;
5) negative pole module and anode pole piece are put into battery container and form battery, the lithium sulfate aqueous solution that implantation concentration is 1mol/l in battery case sealing are to obtain complete battery.
Example 2.
1) positive electrode is 80% LiMn2O4,10% polytetrafluoroethylene, 10% acetylene black mixing, stirs into uniform slurry, and slurry is coated in nickel foam and through compressing tablet becomes anode pole piece, and pole piece thickness is 600 microns;
2) negative material is that 80% graphite, 10% polytetrafluoroethylene, 10% acetylene black are mixed, and stirs into uniform slurry, and slurry is coated on foam copper and compressing tablet preparation becomes cathode pole piece, and capacity of negative plates is positive electrode capacity 120%;
3) cathode pole piece coated outside polypropylene (PP) barrier film, PP barrier film and cathode pole piece all saturated adsorption by the organic bath that is dissolved in lithium hexafluoro phosphate that vinyl carbonate that mass ratio is 1:1 and the concentration in Methylethyl carbonic ester mixed solvent are 1mol/l and prepares;
4) 3) prepare in the anodic aluminium oxide membrane that product is wrapped in rigidity and sealing to obtain negative pole module;
5) negative pole module and anode pole piece are put into battery container and form battery, the lithium sulfate aqueous solution that implantation concentration is 1mol/l in battery case sealing are to obtain complete battery.
Example 3.
1) positive electrode is 80% ferric flouride, 10% polytetrafluoroethylene, 10% acetylene black mixing, stirs into uniform slurry, and slurry is coated on compressing tablet in nickel foam becomes anode pole piece, and pole piece thickness is 1000 microns;
2) the lithium sheet that cathode pole piece is 200 microns by thickness forms;
3) cathode pole piece coated outside adds polyethylene glycol oxide (PEO) and the lithium salts lithium perchlorate (LiClO of polymerized thylene carbonate propylene (polypropylene carbonate) modification
4) polymer dielectric that mix to form;
4) 3) prepare in the anodic aluminium oxide membrane that product is wrapped in rigidity and sealing to obtain negative pole module;
5) negative pole module and anode pole piece are put into battery container and form battery, the water lithium chloride solution that implantation concentration is 1mol/l in battery case sealing are to obtain complete battery.
Refer to Figure 15 and Figure 16, Figure 15 is the charging and discharging curve of example 1 lithium ion battery of the present invention, and as can be seen from Figure 15, this lithium ion battery can discharge and recharge under 20C and the large electric current of 60C, and still has higher capacity under 20C and the large electric current of 60C.Figure 16 is the circulation electricity curve of the 1C of example 1 lithium ion battery, from Figure 16, can find out, this lithium ion battery still has higher capability retention after 50 circulations.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (17)
1. a negative pole module, can be applicable to lithium battery, it is characterized in that, comprise: a negative plate, one organic bath and one first barrier film, described the first barrier film formation one is space independently, and described organic bath is filled in described first in film formed independently space, described negative plate is immersed in described organic bath, and arranges with described the first barrier film interval.
2. negative pole module as claimed in claim 1, is characterized in that, described negative pole module further comprises that one second barrier film is wrapped in described negative plate surface.
3. negative pole module as claimed in claim 1, is characterized in that, described the first barrier film is rigid diaphragms.
4. negative pole module as claimed in claim 1, is characterized in that, the thickness of described negative plate is that 100 μ m are to 1000 μ m.
5. a lithium battery, comprise: a positive pole, a water system electrolyte and the negative pole module as described in claim 1 to 4 any one, described negative pole module and described anodal interval arrange, and described water system electrolyte is at least arranged between described negative pole module and described positive pole.
6. lithium battery as claimed in claim 5, is characterized in that, described water system electrolyte is liquid water system electrolyte.
7. lithium battery as claimed in claim 5, is characterized in that, described negative pole module and described anodal infiltration in described liquid water system electrolyte.
8. lithium battery as claimed in claim 6, is characterized in that, further comprises an electrolyte carrier, and described liquid water system electrolyte is attracted in described electrolyte carrier.
9. lithium battery as claimed in claim 8, is characterized in that, described positive pole and described negative pole module are all arranged on described electrolyte carrier inside.
10. lithium battery as claimed in claim 8, is characterized in that, described positive pole is arranged on described electrolyte carrier inside and forms an anodal module, this positive pole module and the stacked setting of described negative pole module.
11. lithium batteries as claimed in claim 8, it is characterized in that, the stacked setting of described positive pole and described electrolyte carrier forms an anodal module, this positive pole module and the stacked setting of described negative pole module, and described electrolyte carrier is arranged between described positive pole and described negative pole module.
12. lithium batteries as claimed in claim 5, is characterized in that, described water system electrolyte is gel state water system electrolyte.
13. lithium batteries as claimed in claim 12, is characterized in that, it is inner that described positive pole and described negative pole module are all arranged on described gel state water system electrolyte.
14. lithium batteries as claimed in claim 12, is characterized in that, described positive pole is arranged on the inner formation of described gel state water system electrolyte one anodal module, this positive pole module and the stacked setting of described negative pole module.
15. lithium batteries as claimed in claim 12, is characterized in that, described gel state water system electrolyte is arranged between described positive pole and described negative pole module.
16. lithium batteries as claimed in claim 5, it is characterized in that, described lithium battery is lithium ion battery, described positive pole comprises positive active material, and described positive active material is one or more in LiMn2O4, layered lithium manganate, lithium nickelate, cobalt acid lithium, LiFePO4, Li, Ni, Mn oxide and the lithium nickel cobalt manganese oxide of the spinel structure of not doping or doping.
17. lithium batteries as claimed in claim 5, is characterized in that, described lithium battery is lithium-air battery, described just very air electrode, and described air electrode comprises catalytic carrier and catalyst.
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| CN104900943A (en) * | 2015-04-26 | 2015-09-09 | 渤海大学 | Plug-in control gel electrolyte lithium empty electric pile and preparation method thereof |
| CN105914348A (en) * | 2016-03-29 | 2016-08-31 | 宁波大学 | Bi<3+>,B<3+> doped copper fluoride positive electrode material coated by gradient structure and used for lithium battery and preparation method thereof |
| CN109952669A (en) * | 2017-04-06 | 2019-06-28 | 株式会社Lg化学 | The manufacturing method of lithium secondary battery |
| CN113764652A (en) * | 2021-10-08 | 2021-12-07 | 南开大学 | Method for protecting metal cathode of water-based battery by hydrophobic organic layer |
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| CN113764652A (en) * | 2021-10-08 | 2021-12-07 | 南开大学 | Method for protecting metal cathode of water-based battery by hydrophobic organic layer |
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Application publication date: 20140423 |