CN106972192A - For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole - Google Patents

For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole Download PDF

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Publication number
CN106972192A
CN106972192A CN201710155541.5A CN201710155541A CN106972192A CN 106972192 A CN106972192 A CN 106972192A CN 201710155541 A CN201710155541 A CN 201710155541A CN 106972192 A CN106972192 A CN 106972192A
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lithium
prefabricated
cathode
electrode
ion
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周海涛
高宏权
袁晓晨
杨建红
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Jiangsu University
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Jiangsu University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/50Electrodes characterised by their materials specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a kind of method and electrolytic cell device, lithium-ion energy storage device for the prefabricated lithium of lithium-ion energy storage device negative pole, designed using lithium ion half-cell type, it is covered on gel polymer electrolyte between lithium cell cathode material and ceramic base solid electrolyte film, good ionic conduction is provided, gel polymer electrolyte can load full battery together with cathode of lithium battery after prefabricated lithium, manufacture poly-lithium battery.Secondly, the electrolytic cell anode is using lithium ion aqueous solution as electrolyte and lithium source, and lithium source materials are extensive, can be that lithium bittern or waste lithium cell lithium reclaim the aqueous solution, it is environment-friendly, it is nontoxic, chemical property is stable, it is not necessary to strict storage and transporting equipment, reduces the cost of prefabricated lithium.

Description

For the method and electrolytic cell device, lithium ion of the prefabricated lithium of lithium-ion energy storage device negative pole Energy storage device
Technical field
The invention belongs to electrochemical field, it is related to and a kind of does not use lithium metal for the prefabricated lithium of lithium-ion energy storage device negative pole The lithium-ion energy storage device that negative pole after method and electrolytic cell device, and prefabricated lithium is constituted.
Background technology
Lithium-ion energy storage device includes lithium ion battery and lithium-ion capacitor, high with higher energy density, puts certainly Electricity is small, has extended cycle life, the advantages of memory-less effect, is widely used in portable electric appts, energy storage communication, space flight, electricity In the field such as motor-car and honourable energy storage.Along with lithium-ion capacitor and Large Copacity sulfenyl, air (oxygen) base and metal oxidation The development of thing base lithium ion battery, the prefabricated lithium of negative electrode of lithium ion battery has become lithium-ion energy storage research and field of industrial production Very important direction of scientific rersearch and sport technique segment.Traditional prefabricated lithium method uses metallic lithium foil or lithium powder for the prefabricated lithium of negative pole. There is inborn shortcoming in this method:First, the production of lithium metal generally uses high temperature fused salt electrolysis method, it is necessary in protective atmosphere It is lower to carry out, the transport of lithium metal and the strict safeguard procedures of preservation needs and equipment requirement, so lithium metal is not saved in itself Environmental protection.Secondly, lithium metal is the excellence conductor of electronics, easily occurs short circuit with negative pole during prefabricated lithium, there is safety Hidden danger.Again, lithium metal chemism is strong, and can be reacted life with the electrolyte and electrolysis additive of spontaneous same prefabricated lithium Into passivating film, the controllability of prefabricated lithium is have impact on, the recycling of lithium metal equally exists difficulty.
The content of the invention
It is the prefabricated lithium of lithium-ion energy storage device negative pole green the invention provides one kind for Shortcomings in the prior art Method and electrolytic cell device, the process of prefabricated lithium uses wider lithium source not against lithium metal, by lithium ion from water-soluble It is directly prefabricated in liquid to arrive lithium-ion energy storage device negative pole, prefabricated lithium technique will be made more environmentally friendly, cheap and safe.
Be the prefabricated lithium of negative pole the process employs a kind of new electrolytic cell device, during need not use lithium metal. Negative pole after prefabricated lithium is matched with positive pole, lithium-ion energy storage device is assembled into, preferable chemical property is shown.
To achieve these goals, technical scheme is as follows.
A kind of electrolytic cell device for the prefabricated lithium of lithium-ion energy storage device negative pole, mainly includes cathode half-cell and anode half Two parts of battery, it is characterised in that:The cathode half-cell includes cathode chamber, the lithium ion battery anode material being placed in cathode chamber Material, gel polymer electrolyte, ceramic base solid electrolyte film, and it is wrapped in the negative electrode glass sock outside cathode chamber;Institute Stating cathode chamber one end has a through hole, the ceramic base solid electrolyte film be located at the through hole of cathode chamber and with the negative electrode Epoxy resin is set to be sealed between room, the gel polymer electrolyte is located at negative material, ceramic base solid electrolyte Between film, the gel polymer electrolyte is combined by polymer, three kinds of components of electrolytic salt and small molecular organic solvent Gel-type system;The ceramic base solid electrolyte film is oxide system NASICON type glass ceramics solid electricity Xie Zhi;
Glass anode chamber of the anodic half-cell including being equipped with lithium ion aqueous solution, the silver being placed in the anode chamber/ Silver chloride reference electrode, titanium collector, inert electrode or sacrificial electrode, the protection gas;The glass anode chamber is tubulose, institute The one end for stating glass anode chamber is connected with the through hole of the cathode chamber end, and the bottom of the anode chamber is logical provided with protective gas Tracheae.
Preferably, the lithium ion aqueous solution is the water-soluble of the aqueous solution, the aqueous solution of lithium sulfate, lithium chloride of lithium nitrate Liquid, the aqueous solution of lithium perchlorate, the lithium of the bittern of lithium or waste lithium cell reclaim the aqueous solution.
Preferably, the titanium collector is corrosion resistant Ti alloy.Electrochemical corrosion can not be produced in salt solution.
Preferably, the inert electrode include carbon paper, analysis oxygen metal oxide, the analysis oxygen metal oxide be titanium, zirconium, Ruthenium, iridium, tin, the oxide of tantalum or wherein two or more hopcalite;The sacrificial electrode can be in saline solution Middle generation electrochemical corrosion, is zinc, iron, tin, lead or copper.
Preferably, the protective gas is nitrogen, argon gas or carbon dioxide.
Preferably, the second seal with elastometic washer is set between the glass anode chamber and the cathode chamber.
Preferably, the cathode chamber is made up of stainless steel bolt and STAINLESS STEEL NUTS, one end tool of the STAINLESS STEEL NUTS There is annular end face, the stainless steel bolt screws in the other end of the STAINLESS STEEL NUTS, and the bottom of the bolt is covered on negative pole Material.
Preferably, the junction of stainless steel bolt and negative electrode glass sock is sealed using the first rubber ring.
Preferably, the negative material is graphite, silicon, germanium, tin, metal oxide, silicon-base alloy, acieral or tinbase Alloy;The metal oxide is the oxide of germanium, tin, titanium, vanadium, manganese, iron, cobalt, nickel, molybdenum or tungsten.
Preferably, the polymer in the gel polymer electrolyte is polyoxyethylene, polymethyl methacrylate, poly- third Alkene nitrile or polyvinylidene fluoride, the electrolytic salt are lithium hexafluoro phosphate, tetrafluoride lithium borate, lithium perchlorate, trifluoromethanesulfonic acid Lithium, double trifluoromethanesulfonimide lithiums or biethyl diacid lithium borate, the small molecular organic solvent are dimethyl carbonate, carbonic acid two Ethyl ester, ethylene carbonate, propene carbonate, 1,3- dioxolanes or 1,2- dimethoxy-ethanes.
For the method for the prefabricated lithium of lithium-ion energy storage device negative pole, it is characterised in that fill lithium ion aqueous solution in anode chamber, Cathode chamber is connected with anode chamber, using the ceramic base solid electrolyte film being placed in inside cathode chamber as lithium ion transport Window, selective prevention hydrone, proton, the ion of hydrated and solvation pass through;Be covered on lithium cell cathode material and Gel polymer electrolyte between ceramic base solid electrolyte film provides good conduction for lithium ion;By negative electrode stainless steel Bolt is connected with the working electrode interface of electrochemical workstation, the titanium of inert electrode or sacrificial electrode will be loaded with anode chamber Collector is connected with electrochemical workstation to electrode interface, by ginseng of the silver/silver chloride reference electrode with electrochemical workstation It is connected than electrode interface, uses the prefabricated lithium of negative pole that the electrochemical method of constant cathode electric current is lithium ion.
Further, use the cathode-current density after the area normalization of ceramic base solid electrolyte film for 1~ 40A/m2, the time required to the shortest time of prefabricated lithium is negative material Surface Creation SEI films, maximum duration is to reach negative material The time required to the biggest quality specific capacity of initial prefabrication lithium.
A kind of lithium-ion energy storage device of negative pole composition after prefabricated lithium of method by prefabricated lithium of the present invention, it is special Levy and be, the negative pole after the prefabricated lithium of method of prefabricated lithium of the present invention is matched with positive pole, lithium-ion energy storage is assembled into Device, the positive electrode used be activated carbon, transition group metallic oxide, sulfenyl, air, oxygen, LiMn2O4, cobalt acid lithium, LiFePO4 or tertiary cathode material.
Compared with prior art, first, the cathode of electrolytic tank uses lithium to the electrolytic cell device of prefabricated lithium of the present invention Ion half-cell type is designed, and lithium cell cathode material and ceramic base solid electrolyte film are covered on gel polymer electrolyte Between there is provided good ionic conduction, gel polymer electrolyte can load full electricity together with cathode of lithium battery after prefabricated lithium Pond, manufactures poly-lithium battery.Secondly, the electrolytic cell anode is used as electrolyte and lithium source, the lithium source using lithium ion aqueous solution Materials are extensive, can be lithium bittern or the waste lithium cell lithium recovery aqueous solution, environment-friendly, nontoxic, chemical property is stable, is not required to Strict storage and transporting equipment are wanted, the cost of prefabricated lithium is reduced.Using inert electrode, generation oxygen or chlorine can be collected Utilize, the hydrogen ion generated in electrolyte can add alkali to neutralize, electrolyte recycling.Using sacrificial electrode, the metal of generation Salting liquid can carry out recycling by the method for chemical precipitation.Again, the negative electrode of the electrolytic cell and anode are using ceramics Base solid electrolyte is used to completely cut off air and water enters negative electrode, and the ceramic base solid electrolyte manufacturing process is ripe, without expensive Metal, is encapsulated into after electrolytic cell, may be reused, and reduce further the cost of prefabricated lithium.The ceramic base solid electrolyte It is the insulator of electronics, effectively prevent short-circuit generation during prefabricated lithium, eliminate potential safety hazard.The ceramic base solid-state Chemical property of the electrolyte in organic electrolyte is stable, will not make prefabricated lithium process with electrolyte and additive spontaneous reaction Controllability enhancing.Finally, the electrochemical process of prefabricated lithium is easy to control the electricity of prefabricated lithium using three electrodes and the method for constant current Pressure, electric current and time, it is easy to control the stoichiometry of prefabricated lithium.
The electrolytic cell device of prefabricated lithium of the present invention is (i.e. ceramic by lithium ion conducting window after engineering amplification Base solid electrolyte) cathode of electrolytic tank end is encapsulated in, prevent moisture from oozing out, lithium ion aqueous solution passes in and out the moon at a flow way Pole, installing aqueous solution recycling system, there is provided enough lithium sources.And the device of prefabricated lithium is integrated into manufacture energy storage device It is further cost-effective in streamline.
The method of prefabricated lithium of the present invention, does not use lithium metal, lithium source is more extensively, cheaply in the process of prefabricated lithium With it is environment-friendly;The process control of prefabricated lithium is strong;High safety, is prevented effectively from the generation of prefabricated lithium short-circuit conditions.It is described pre- The electrolytic cell device and method of lithium processed can be widely used for the prefabricated lithium of integrated circuit micro cell, the prefabricated lithium of lithium-ion capacitor, or Negative electrode of lithium ion battery chemical conversion and lithiumation etc., are carried to manufacture safer, environment-friendly and Large Copacity lithium-ion energy storage equipment Technical strategies are supplied.
Negative pole after the prefabricated lithium of method of prefabricated lithium of the present invention is matched with positive pole, lithium-ion energy storage is assembled into Device, shows higher specific discharge capacity and preferable cycle performance.It is assembled into the positive pole that lithium-ion energy storage device is used Material is the oxide of activated carbon, transition group metallic oxide, such as vanadium, manganese, iron or cobalt, sulfenyl, air or oxygen, LiMn2O4, Cobalt acid lithium, LiFePO4 or tertiary cathode material etc..
Brief description of the drawings
Fig. 1 is the schematic diagram of the electrolytic cell device of the present invention for being the prefabricated lithium of lithium-ion energy storage device negative pole.
Continuity schematic device after electrolytic cell engineering described in Fig. 2.
Fig. 3 is to the curve of the prefabricated lithium of silicon substrate cathode of lithium battery constant current in example 1 using Novel electrolytic tank.
Fig. 4 is the first charging and discharging curve for the full battery of manganese oxide/silicon lithium ion tested in example 1, and the negative pole is use Silicon substrate cathode of lithium battery after the prefabricated lithium of new method.Show higher specific discharge capacity.
Fig. 5 is the first charging and discharging curve for the full battery of sulphur/silicon lithium ion tested in example 2, and the negative pole is using new side Silicon substrate cathode of lithium battery after the prefabricated lithium of method.
Fig. 6 is to the curve of the prefabricated lithium of silicon substrate cathode of lithium battery constant current in example 1 using Novel electrolytic tank.
Fig. 7 is the first charging and discharging curve for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 3, and the negative pole is Using the manganese oxide base cathode of lithium battery after the prefabricated lithium of new method.
Fig. 8 is the cycle performance for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 3.
Fig. 9 is the first charging and discharging curve for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 4, and the negative pole is Using the manganese oxide base cathode of lithium battery after the prefabricated lithium of new method.
Figure 10 is the cycle performance for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 4.
In figure:1st, negative material, 2, gel polymer electrolyte, 3, ceramic base solid electrolyte film, 4, stainless steel spiral shell Cap cathode chamber, 5, epoxy resin, 6, negative electrode glass sock, 7, stainless steel bolt, 8, rubber ring, 9, rubber ring, 10, fill lithium ion The glass anode chamber of the aqueous solution, 11, silver/silver chloride reference electrode, 12, titanium collector, 13, inert electrode or sacrificial electrode, 14, Protective gas breather pipe.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously Not limited to this.
As shown in figure 1, the electrolytic cell device of the present invention for the prefabricated lithium of lithium-ion energy storage device negative pole, mainly includes Two parts of cathode half-cell and anodic half-cell.The cathode half-cell includes cathode chamber 4, the lithium electricity being placed in cathode chamber 4 Pond negative material 1, gel polymer electrolyte 2, ceramic base solid electrolyte film 3, and it is wrapped in the moon outside cathode chamber 4 Pole glass sock 6.The outside negative electrode glass sock 6 of cathode chamber, which is wrapped up, to be caused on the outside of cathode chamber waterproof and is electrically insulated.The cathode chamber 4 One end has through hole, and the ceramic base solid electrolyte film 3 is located at the through hole of cathode chamber 4 and between the cathode chamber 4 Epoxy resin 5 is set to be sealed, to prevent air and water from entering in cathode chamber 4,.The ceramic base solid electrolyte film 3 be oxide system NASICON type glass ceramics solid electrolytes, and its component includes lithium, aluminium, titanium, silicon, phosphorus, germanium and oxygen.Ceramics Base solid electrolyte film is as the window of lithium ion transport, and hydrone, proton, the ion of hydrated and solvation can not lead to Cross.The gel polymer electrolyte 2 is located between negative material 1, ceramic base solid electrolyte film 3, the gel polymerisation Thing electrolyte is the gel-type system being composited by polymer, three kinds of components of electrolytic salt and small molecular organic solvent.Specifically , the cathode chamber 4 is made up of stainless steel bolt and STAINLESS STEEL NUTS, and one end of the STAINLESS STEEL NUTS has annular end face, The stainless steel bolt screws in the other end of the STAINLESS STEEL NUTS, and the bottom of the bolt is covered on negative material 1.Stainless steel The junction of bolt and negative electrode glass sock is sealed using the first rubber ring 8, to prevent air and water from entering cathode chamber 4.
The anodic half-cell includes the glass anode chamber 10 equipped with lithium ion aqueous solution, is placed in the anode chamber 10 Silver/silver chloride reference electrode 11, titanium collector 12, inert electrode or sacrificial electrode 13, the protection gas 14;The glass anode Room 10 is tubulose, and one end of the glass anode chamber 10 is connected with the through hole of the end of cathode chamber 4, the glass anode The second rubber ring 9 is set to seal between room 10 and the cathode chamber 4, the spilling for preventing lithium ion aqueous solution.The glass Lithium ion aqueous solution in anode chamber 10 is the aqueous solution, the aqueous solution of lithium sulfate, the aqueous solution of lithium chloride, the perchloric acid of lithium nitrate The lithium of the aqueous solution of lithium, the bittern of lithium or waste lithium cell reclaims the aqueous solution.The bottom of the anode chamber 10 is provided with protective gas Breather pipe 14, is passed through nitrogen, argon gas or carbon dioxide, for stirring lithium ion aqueous solution so that in electricity to the anode chamber 10 The concentration of the lithium ion of solution in chemical process is more uniform.
Embodiment 1
For for the prefabricated lithium of silicon substrate lithium cell cathode material, first by electrolytic cell device of the present invention according to Fig. 1 groups Dress.First, the negative electrode of electrolytic cell is assembled in the glove box full of argon gas, the gel electrolyte used is 3 for infiltration volume ratio: 7 1M LiPF6PVDF/PMMA/PVDF in EC/DE C organic electrolytes, is placed in STAINLESS STEEL NUTS, and be covered on Ceramic base solid electrolyte film, the ceramic base solid electrolyte film used is Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2 Glass ceramic film.Silicon-based anode is covered on gel electrolyte, screwed after stainless steel bolt.Then by the same glass of cathode of electrolytic tank Glass anode assembling is to together, using the second seal with elastometic washer.Ag/AgCl reference electrodes and the titanium rod for being wound with copper cash are placed in glass Glass anode, 0.5MLi is poured into glass anode2SO4The aqueous solution, and argon gas is passed through, device assembling is finished.It is with wire that negative electrode is stainless Steel bolt is connected with the working electrode interface of electrochemical workstation, and titanium rod is connected with to electrode interface, Ag/AgCl is joined It is connected than electrode with reference electrode interface.Using constant cathode electric current to the prefabricated lithium of silicon-based anode, using ceramic base solid-state electricity Solve after the thin area normalization of matter, cathode-current density is 2A/m2, the time of prefabricated lithium is 4.2 hours, and the silicon-based anode is new The curve of the prefabricated lithium of constant current is shown in Fig. 3 in type electrolytic cell.After prefabricated lithium terminates, negative electrode is opened in glove box, after prefabricated lithium Silicon-based anode and gel polymer electrolyte are taken out together, and battery, both positive and negative polarity active material are helped with oxidation manganese-based anode assembling Mass ratio be 6:1, volume ratio is used for 3:7 1M LiPF6EC/DEC is used as organic electrolyte.The full battery is in C/10 (1 C=150mA/g, by both positive and negative polarity active material gross mass calculate) under initial discharge specific discharge capacity be 249mAh/g, see figure It is the 50% of initial capacity after 4,0.5C circulations 100 times.
Embodiment 2
For for the prefabricated lithium of silicon substrate lithium cell cathode material, the present apparatus is assembled according to Fig. 1 first.First, full of argon The negative electrode of electrolytic cell is assembled in the glove box of gas, the gel electrolyte used is 3 in volume ratio for infiltration:7 1M LiPF6EC/ PVDF/PMMA/PVDF in DEC organic electrolytes, is placed in STAINLESS STEEL NUTS, and is covered on ceramic base solid state electrolysis Matter film, the ceramic base solid electrolyte film used is Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2Glass ceramic film.By silicon Base negative pole is covered on gel electrolyte, is screwed after stainless steel bolt.Then by cathode of electrolytic tank with glass anode assembling to one Rise, using the second seal with elastometic washer.Ag/AgCl reference electrodes and the titanium rod for being wound with copper cash are placed in glass anode, to glass Anode pours into 0.5MLi2SO4The aqueous solution, and argon gas is passed through, device assembling is finished.With wire by negative electrode stainless steel bolt with electrification The working electrode interface for learning work station is connected, and titanium rod is connected with to electrode interface, by the same reference of Ag/AgCl reference electrodes Electrode interface is connected.Using constant cathode electric current to the prefabricated lithium of silicon-based anode, using the thin area of ceramic base solid electrolyte Cathode-current density after normalization is 2A/m2, the time of prefabricated lithium is 5.2 hours.After prefabricated lithium terminates, beaten in glove box Negative electrode is opened, the silicon-based anode after prefabricated lithium is taken out, battery, the mass ratio of both positive and negative polarity active material are helped with sulfur-based positive electrode assembling For 2:1, using volume ratio 3:7 organic electrolyte 1M LiPF6EC/DEC.The full battery (presses both positive and negative polarity active matter in 33mA/g The gross mass of matter is calculated) under initial discharge specific discharge capacity be 693mAh/g, see Fig. 5.
Embodiment 3
For for the prefabricated lithium of manganese oxide base lithium cell cathode material, the present apparatus is assembled according to Fig. 1 first.First, filling The negative electrode of electrolytic cell is assembled in the glove box of full argon gas, the gel electrolyte used is infiltration in volume ratio 3:7 1M LiPF6
PVDF/PMMA/PVDF in EC/DEC organic electrolytes, is placed in STAINLESS STEEL NUTS, and is covered on ceramics Base solid electrolyte film, the ceramic base solid electrolyte film used is Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2Glass Ceramic membrane.Manganese oxide base negative pole is covered on gel electrolyte, screwed after stainless steel bolt.Then by the same glass of cathode of electrolytic tank Glass anode assembling is to together, using seal with elastometic washer.Ag/AgCl reference electrodes and the titanium rod for being wound with copper cash are placed in glass sun Pole, 0.5MLi is poured into glass anode2SO4The aqueous solution, and argon gas is passed through, device assembling is finished.With wire by negative electrode stainless steel spiral shell Bolt is connected with the working electrode interface of electrochemical workstation, and titanium rod is connected with to electrode interface, by Ag/AgCl references electricity Extremely it is connected with reference electrode interface.Using constant cathode electric current to the prefabricated lithium of silicon-based anode, cathode-current density is 4A/m2 (after the thin area normalization of ceramic base solid electrolyte), the time of prefabricated lithium is 42min.The manganese oxide base negative pole is new The curve of the prefabricated lithium of constant current is shown in Fig. 6 in type electrolytic cell.After prefabricated lithium terminates, negative electrode is opened in glove box, after prefabricated lithium Manganese oxide base negative pole takes out, and helps battery with the assembling of LiMn2O4 base positive pole, the mass ratio of both positive and negative polarity active material is 5:1, use Volume ratio 3:7 obtain 1M LiPF6EC/DEC organic electrolytes.The full battery (presses total matter of both positive and negative polarity active material in 33mA/g Amount calculate) under initial discharge specific discharge capacity be 57mAh/g, see Fig. 7.It is the 47% of initial capacity after circulating 100 times, sees figure 8。
Embodiment 4
For the prefabricated lithium of metal aluminum foil negative pole, using the continuity device after engineering, as shown in Figure 2.First, this is continuous Property device run under protective atmosphere, the gel electrolyte used be infiltration in volume ratio 3:7 1M LiPF6EC/DEC is organic The ceramic base solid electrolyte film used in PVDF/PMMA/PVDF in electrolyte, lithium ion window is Li2O-Al2O3- SiO2-P2O5-TiO2-GeO2Oxygen electrode is analysed using titanium oxide inertia by glass ceramic film, anode chamber, and lithium source is 0.5 M Li2SO4 The aqueous solution.By roll-to-roll mode, gel electrolyte is covered on metal aluminum foil negative pole, lithium ion beneath window is entered. Lithium ion window, which is pushed, to be pasted with gel electrolyte, turn-on current between oxygen anodes and aluminium foil is analysed in inertia, and cathode current is close Spend for 40A/m2(after the thin area normalization of ceramic base solid electrolyte), the time of prefabricated lithium is 4min.Prefabricated lithium knot Lifted on Shu Hou, lithium ion window, the aluminium foil section after prefabricated lithium removes lithium ion window region with roller, pastes and is assembled into carbon-based positive pole Full battery, using volume ratio 3:7 obtain 1M LiPF6EC/DEC organic electrolytes.The full battery is in 100mA/g (by both positive and negative polarity activity The gross mass of material is calculated) under initial discharge specific discharge capacity be 150mAh/g, see Fig. 9.It is initial hold after circulating 2000 times The 97% of amount is shown in Figure 10.
For the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment to the embodiment, not In the case of the substantive content of the present invention, any conspicuously improved, replacement that those skilled in the art can make Or modification belongs to protection scope of the present invention.

Claims (10)

1. a kind of electrolytic cell device for the prefabricated lithium of lithium-ion energy storage device negative pole, mainly includes cathode half-cell and the electricity of anode half Two, pond part, it is characterised in that:The cathode half-cell includes cathode chamber (4), the cathode of lithium battery being placed in cathode chamber (4) Material (1), gel polymer electrolyte (2), ceramic base solid electrolyte film (3), and it is wrapped in cathode chamber (4) outside Negative electrode glass sock (6);Described cathode chamber (4) one end has through hole, and the ceramic base solid electrolyte film (3) is located at cathode chamber (4) through hole and epoxy resin (5) is set to be sealed between the cathode chamber (4), the gel polymer electrolyte (2) it is located between negative material (1), ceramic base solid electrolyte film (3), the gel polymer electrolyte is by polymerizeing The gel-type system that thing, three kinds of components of electrolytic salt and small molecular organic solvent are composited;The ceramic base solid electrolyte Film (3) is oxide system NASICON type glass ceramics solid electrolytes;
The anodic half-cell includes the glass anode chamber (10) equipped with lithium ion aqueous solution, is placed in the anode chamber (10) Silver/silver chloride reference electrode (11), titanium collector (12), inert electrode or sacrificial electrode (13), the protection gas (14);It is described Glass anode chamber (10) is tubulose, and one end of the glass anode chamber (10) is connected with the through hole of the cathode chamber (4) end, The bottom of the anode chamber (10) is provided with protective gas breather pipe (14).
2. electrolytic cell device according to claim 1, it is characterised in that:The lithium ion aqueous solution is water-soluble for lithium nitrate Liquid, the aqueous solution of lithium sulfate, the aqueous solution of lithium chloride, the aqueous solution of lithium perchlorate, the lithium of the bittern of lithium or waste lithium cell are returned Receive the aqueous solution.
3. electrolytic cell device according to claim 1, it is characterised in that:The inert electrode includes carbon paper, analysis oxygen metal Oxide, the analysis oxygen metal oxide is titanium, zirconium, ruthenium, iridium, tin, the oxide of tantalum or wherein two or more oxide Mixture;Electrochemical corrosion can occur in saline solution for the sacrificial electrode, be zinc, iron, tin, lead or copper.
4. electrolytic cell device according to claim 1, it is characterised in that:The glass anode chamber (10) and the cathode chamber (4) the second rubber ring (9) is set to seal between, the junction of stainless steel bolt and negative electrode glass sock uses the first rubber ring (8) Sealed.
5. electrolytic cell device according to claim 1, it is characterised in that:The cathode chamber (4) is by stainless steel bolt and not The steel nut that becomes rusty is constituted, and one end of the STAINLESS STEEL NUTS has annular end face, and the stainless steel bolt screws in the stainless steel spiral shell The other end of cap, the bottom of the bolt is covered on negative material (1).
6. electrolytic cell device according to claim 1, it is characterised in that:The negative material is graphite, silicon, germanium, tin, gold Belong to oxide, silicon-base alloy, acieral or kamash alloy;The metal oxide be germanium, tin, titanium, vanadium, manganese, iron, cobalt, nickel, The oxide of molybdenum or tungsten.
7. electrolytic cell device according to claim 1, it is characterised in that:Polymer in the gel polymer electrolyte For polyoxyethylene, polymethyl methacrylate, polyacrylonitrile or polyvinylidene fluoride, the electrolytic salt be lithium hexafluoro phosphate, Tetrafluoride lithium borate, lithium perchlorate, trifluoromethanesulfonic acid lithium, double trifluoromethanesulfonimide lithiums or biethyl diacid lithium borate, it is described Small molecular organic solvent be dimethyl carbonate, diethyl carbonate, ethylene carbonate, propene carbonate, 1,3- dioxolanes or 1,2- dimethoxy-ethanes.
8. electrolytic cell device according to claim 1 is the method for the prefabricated lithium of lithium-ion energy storage device negative pole, its feature exists In, lithium ion aqueous solution is filled in anode chamber, cathode chamber is connected with anode chamber, it is solid using the ceramic base being placed in inside cathode chamber State electrolytic thin-membrane is used as the window of lithium ion transport, the selective ion for preventing hydrone, proton, hydrated and solvation Pass through;The gel polymer electrolyte being covered between lithium cell cathode material and ceramic base solid electrolyte film is lithium ion Good conduction is provided;Negative electrode stainless steel bolt (7) is connected with the working electrode interface of electrochemical workstation, by anode chamber In be loaded with inert electrode or the titanium collector (12) of sacrificial electrode (13) is connected with electrochemical workstation to electrode interface, Silver/silver chloride reference electrode is connected with the reference electrode interface of electrochemical workstation, the electrification of constant cathode electric current is used Method is the prefabricated lithium of negative pole of lithium ion.
9. the method for prefabricated lithium according to claim 8, it is characterised in that using ceramic base solid electrolyte film (3) Area normalization after cathode-current density be 1~40A/m2, the shortest time of prefabricated lithium is negative material Surface Creation SEI The time required to film, the time required to maximum duration is the biggest quality specific capacity for reaching negative material initial prefabrication lithium.
10. the lithium-ion energy storage device of the negative pole composition after the prefabricated lithium of method of prefabricated lithium according to claim 9, it is special Levy and be, the negative pole after the prefabricated lithium is matched with positive pole, lithium-ion energy storage device is assembled into, the positive electrode used It is activated carbon, transition group metallic oxide, sulfenyl, air, oxygen, LiMn2O4, cobalt acid lithium, LiFePO4 or tertiary cathode material Material.
CN201710155541.5A 2017-03-16 2017-03-16 For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole Pending CN106972192A (en)

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