CN106207091A - A kind of lithium ion battery flexibility positive pole, its preparation method and the super full battery of flexible lithium ion - Google Patents

A kind of lithium ion battery flexibility positive pole, its preparation method and the super full battery of flexible lithium ion Download PDF

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Publication number
CN106207091A
CN106207091A CN201610655022.0A CN201610655022A CN106207091A CN 106207091 A CN106207091 A CN 106207091A CN 201610655022 A CN201610655022 A CN 201610655022A CN 106207091 A CN106207091 A CN 106207091A
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flexible
lithium
positive pole
electrode
carbon
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王建
马子涵
张会刚
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Nanjing University
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Nanjing University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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

Abstract

The invention provides a kind of lithium ion battery flexibility positive pole, its preparation method and the super full battery of flexible lithium ion, the lithium ion battery flexibility positive pole of the present invention is the integration formed by lithium cell anode material lithium manganate (650) and flexible back bone (150) solely stone electrode.The preparation method of flexible positive pole includes following two steps: 1) selects a kind of flexible back bone, uses plating mode to deposit hydroxide oxygen manganese material on flexible back bone；2) the hydroxide oxygen manganese material of electro-deposition lithiumation in the fused salt containing lithium ion of low melting point is processed, define the lithium cell anode material lithium manganate that conformal (conformal) is grown on flexible back bone.The present invention has the following technical effect that and present invention uses three-dimension flexible network or support as matrix, and flexible substrate can accept significantly deformation in BENDING PROCESS.

Description

A kind of lithium ion battery flexibility positive pole, its preparation method and super flexible lithium ion are complete Battery
Technical field
The invention belongs to inorganic functional material preparation field, be specifically related to a kind of lithium ion battery flexibility positive pole, it prepares Method and the super full battery of flexible lithium ion.
Background technology
Along with the progress of intelligence science and technology, various flexible apparatus also become the main force of electronic market.Current flexibility Equipment mainly has flexible display, radio-frequency card, intelligent wearable product and sensor etc..But flexible battery technology is slow Development, becomes restraining factors of high-end flexible electronic devices development.Existing conventional batteries the most all has rigidity and thickness Shortcoming in terms of degree, limits its use in fexible film apparatus field.So, be badly in need of developing a kind of super flexible lithium from The full battery of son.
Battery is mainly made up of these constituent elements of electrode, electrolyte, barrier film and shell, and wherein the preparation of flexible electrode is researched and developed then It it is the key point of whole flexible battery.And current business positive pole (negative pole) material, mainly cobalt acid lithium, LiMn2O4, phosphoric acid Ferrous lithium (graphite, lithium titanate) etc..Traditional preparation process, is all by positive pole (negative pole) material and conductive agent (acetylene black, section's qin Black, super P etc.), binding agent (polyvinylidene fluoride, politef etc.), the additive mix and blend such as thickening agent form slurry, And by slurry coating on flexible aluminium foil or Copper Foil, make electrode slice.Such as: Chinese patent CN104681858A uses aluminium foil It is mixed with out a kind of ultrathin flexible lithium ion battery with active substance binding agent etc..But the active material particle of these rigidity with And metal collector can occur active substance to peel off and come off etc. problem when Bending Deformation, cause that electrode slice is damaged, pierce through every The situations such as film, make battery failure.Thus the needs of flexible apparatus can not be met, limit the development of flexible battery.
For improving further the flexibility of battery, existing many work mainly uses with carbon nano-tube film, Graphene thin Films etc. come substituted metal collector or the method using CNT and active substance physical mixed film forming.Such as Chinese patent CN104485478A provides a kind of fexible film prepared with Graphene or CNT, and on use traditional handicraft to enter Row coating active material, forms flexible electrical pole piece and prepares battery.Also there is similar method (ACS Nano, 10 (4) 5843- 5848 (2010)) prepare fexible film with CNT to be coated, prepare paper-like battery.The method can change to a certain extent The flexibility of kind battery, promote its mechanical performance but still be use binding agent to connect collector and active substance, at deformation process Coming off of middle active substance is also inevitable, thus affects lithium electrical property.Further ameliorative way is to prepare one without viscous The self-supporting system of knot agent, general uses the method such as sucking filtration film forming or solvent evaporation film forming, as in patent CN102593436 with carbon Nanotube dust and active particle carry out sucking filtration after dispersion mixing, form composite and flexible electrode material. Electrochemistry Communications(2011,13,383-386) report with multi-walled carbon nano-tubes and V2O5's Mixed solution dispersion sucking filtration forms the flexible electrode of self-supporting.Nano Energy (2015,12,43-51) reports with nickel Manganese binary positive material forms high performance lithium ion anode material with multi-walled carbon nano-tubes mixing sucking filtration.With regard to solvent evaporation Speech, Energy Environmental Science (2012,5,6845-6849) reports employing CNT and vanadic acid Ammonium is combined hydro-thermal, forms CNT and V2O5The mixed solution of nano wire, vacuum drying has obtained CNT and V2O5Compound High performance flexible electrode.Materials Research Bulletin (2013,48,3713-3716) reports Carry out vacuum drying with the mixed solution of Graphene and LiFePO4 and obtain the complex three-dimensional structures electricity of Graphene and LiFePO4 Pole.These methods, while can obtain overall electrode material while using avoiding binding agent, but these active substances are only It is embedded at random in conductive network, in deformation, good contacting can not be kept with skeleton, reduce the utilization of active substance Rate, the stress of granule can not be transferred in flexible back bone simultaneously, thus have impact on battery electrochemistry in deformation process Performance and mechanical performance.
Technology based on existing flexible battery both shortcomings, the present invention proposes the preparation side of a kind of novel flexible electrode material Method, improves flex capability and the chemical property of battery further, promotes improving further and sending out of lithium ion battery level Exhibition.
Summary of the invention
The goal of the invention of the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of lithium ion battery flexibility positive pole, its system Preparation Method and the super full battery of flexible lithium ion, solve conventional batteries drawback in terms of flexibility, meets flexible apparatus development Requirement.
In the present invention, the mentality of designing for the flexible positive pole of lithium ion battery is by using the skeleton of a kind of flexibility Accept stress, by positive pole ceramic material growth in situ to the method on flexible back bone being formed a kind of composite construction, this multiple Composite electrode has kernel and the shell of hard of flexibility.This nucleocapsid structure at nanoscale in substance form a doubly-linked Continuous network.Flexible skeleton is conductive net, and hard shell is active material network, and the two soft or hard combines and forms integration Electrode.By bending process, Stress Transfer to flexible soft kernel, is deformed upon by the shell of hard, and actually shell is with interior There is the relative displacement of minimum degree between portion's skeleton, thus maintain electronic conduction, maintain higher battery performance.
First goal of the invention of the present invention is to provide a kind of lithium ion battery flexibility positive pole, and described lithium ion battery is soft Property positive pole be the integration solely stone electrode formed by lithium cell anode material lithium manganate (650) and flexible back bone (150), institute State monolithic structure to refer in electrode that various components are interted and form an overall structure, rather than loosely, random stacking states.
In described flexible positive pole, lithium cell anode material lithium manganate (650) conformal growth is in flexible back bone (150) On, described conformal lithium cell anode material lithium manganate (650) material morphology structure replication flexible back bone (150) of referring to External surface shape, uniformity on skeleton, form the network of a kind of co-continuous, one of them continuous phase is active material, Another continuous phase is conductive flexible skeleton.
Described lithium cell anode material lithium manganate (650) use electro-deposition and the preparation of fused salt lithiumation two-step method and Becoming, so-called flexible back bone (150) is selected from flexible carbon material.
Described flexible carbon material is carbon nanometer paper, CNT, Buckie paper, carbon fiber, carbon felt, carbon cloth or the fibre of carbonization Wei Bu.
Second goal of the invention of the present invention is to provide the preparation method of above-mentioned flexible positive pole, including following two steps:
1) select a kind of flexible back bone, use plating mode to deposit hydroxide oxygen manganese material on flexible back bone；
2) the hydroxide oxygen manganese material of electro-deposition lithiumation in the fused salt containing lithium salts of low melting point is processed, define conformal life Long lithium cell anode material lithium manganate on flexible back bone.
The detailed process of described step 1) is as follows: select working electrode (100), by working electrode (100) with to electrode (200) being inserted in the electroplate liquid (300) containing divalent manganesetion, electroplating process selects reference electrode (350), or only with containing Have working electrode (100) and two electrode systems to electrode (200) to carry out electro-deposition, electro-plating method use constant current, constant voltage, Cyclic voltammetric or pulse constant current constant voltage mode, after having deposited, take out working electrode (100), rinse electrode surface It is dried after removing soluble-salt.Concrete electroplating process is as shown in Figure 1.
Described step 2) detailed process as follows:
1) by a certain proportion of lithium salt, put into and crucible (400) is heated to 180 ~ 300 ° of C, until melting completely, Then the dried working electrode (100) treating lithiumation is carried out lithiumation in being completely submerged in fused salt (500)；
2) after lithiumation has processed, being taken out by the working electrode of lithiumation, clean with deionized water, drying for standby, gained is soft Property positive pole (600).
Described working electrode (100) is selected from flexible carbon material, can be CNT, carbon nanometer paper, Buckie paper, carbon fibre Dimension, carbon felt, carbon cloth, the flexible carbon material such as fiber cloth of carbonization.Fig. 2 shows the flexible bone used by the present invention as a example by carbon nanometer paper Frame is made up of the carbon nano tube flexible skeleton (150) that can bend, and plating and lithiumation complete each carbon nano tube flexible afterwards All conformal deposited LiMn2O4 (650) on skeleton (150).
Described is conductive material to electrode (200), optional metal or graphite cake or other material with carbon elements.Metal electrode, Can be Ni, Cu, Pt, Au etc., must be handled as follows before electrochemical deposition: use dilute hydrochloric acid to remove oxide on surface Layer, then uses deionized water rinsing, is positioned over drying for standby in 70 DEG C of baking ovens.Carbon nanomaterial can be CNT, carbon Nanofiber, carbon nano-cloth etc..Because the preparation method of different material with carbon elements is different, it may be necessary to carry out high temperature before electrochemical deposition Process, to remove skim-coat organic impurities or catalyst.
Described electroplate liquid (300) includes containing 0.01 ~ 3M divalent manganesetion compound (such as manganese sulfate or manganese acetate), also Including one or more in additive sodium sulfate, sodium acetate, ammonium acetate.
Described fused salt includes one or more in lithium nitrate, Lithium hydrate, lithium chloride.
Described fused salt includes that lithium nitrate and Lithium hydrate, described lithium nitrate and Lithium hydrate mass ratio are 4:(1.7- 4), wherein moisture at 0 ~ 20wt%.
3rd goal of the invention of the present invention is to provide a kind of full battery of super flexible lithium ion containing described flexible positive pole, Including sealing flexible package bag, being located at and seal the assembly that flexible package bag is internal, described assembly by the porous battery of centre every Film, be located at porous battery diaphragm side flexibility positive pole, be located at porous battery diaphragm other side flexible carbon nano tube negative pole or Person's graphited carbon fiber negative electrode layer is stacked, and is provided with electrolyte between described flexible package bag and assembly.
The full battery of super flexible lithium ion of the present invention uses traditional soft-package battery technique, by the flexibility prepared by the present invention Positive pole, porous battery diaphragm, flexible carbon nano tube negative pole or three kinds of component layer of graphited carbon fiber negative pole gather into folds, and load In flexible Soft Roll shell, carry out vacuum sealing and note electrolyte, the operation such as chemical conversion.
Compared with prior art, the present invention has the following technical effect that
1, present invention uses three-dimension flexible network or support as matrix, flexible substrate can accept greatly in BENDING PROCESS Amplitude deformation.
2, the present invention is on flexible back bone surface, deposited active substance, anode material for lithium-ion batteries, phase by two-step method To more crisp, it is impossible to bending, but active positive electrode material is conformal to be attached to above flexible back bone, owing to the feature of electrodeposition process is protected Demonstrate,prove this attachment the most firm.During bending, whole combination electrode there occurs deformation, but at inside battery positive pole pottery Stress is forwarded to flexible back bone by material, skeleton accepts deformation, it is to avoid the brittle failure of positive electrode.
3, conventional high-temperature solid phase synthesis LiMn2O4, temperature can have the highest temperature between 700 DEG C to 900 DEG C.This The temperature that bright fused salt processes is substantially reduced compared to conventional art, effectively reduces energy loss.Meanwhile, close relative to high temperature solid-state The regulation and control parameter of one-tenth method is single, and electro-deposition and molten-salt growth method have widely parameter modification scope.
The present invention uses flexible 3 D material with carbon element to be that substrate prepares can folding use soft in normal use process Property positive pole and super flexible lithium ion battery.This battery may be used for film type smart machine, such as wearable device, implantable life Thing equipment, radio-frequency card etc. aspect, has saved the space of flexible apparatus, thus has promoted the development of flexible apparatus.
Accompanying drawing explanation
Fig. 1 is the preparation technology schematic diagram of the flexible positive pole of the present invention.
Fig. 2 is the present invention conformal schematic diagram shown in as a example by CNT.
Fig. 3 is CNT former state scanning electron microscope diagram.
Fig. 4 is the scanning electron microscope diagram of intermediate product after plating step.
Fig. 5 is after fused salt processes step, the scanning electron microscope diagram of positive electrode.
Fig. 6 is the XRD diffracting spectrum of positive electrode.
Fig. 7 is that lithium electrode carries out 500mA/g constant current charge-discharge test, the charge and discharge under 2.0V to 4.1V voltage window The data of electricity circulation.
Fig. 8 is the 500mA/g constant current charge-discharge test entering full battery, the charge and discharge under 2.0V to 4.1V voltage window The data of electricity circulation.
Fig. 9 is the datagram at 0 ~ 180 ° of reciprocal folding times Yu capability retention characterizing full cell flexible.
Figure 10 is the scanning electron microscope diagram of intermediate product after 1.4V plating step.
Figure 11 is after 1.4V electrode fused salt processes step, the scanning electron microscope diagram of positive electrode.
Figure 12 is the XRD diffracting spectrum of 1.4V positive electrode.
Figure 13 is the 500mA/g constant current charge-discharge test after fused salt processes after 0.75V constant voltage pulse, arrives at 2.0V The data of the charge and discharge circulation of 4.1V.
Figure 14 is the 500mA/g constant current charge-discharge test after fused salt processes after 1.4V constant voltage pulse, arrives at 2.0V The data of the heavily charge and discharge circulation of 4.1V.
Figure 15 is the number at 0 ~ 180 ° of reciprocal folding times Yu capability retention characterizing full cell flexible prepared by 1.4V According to figure.
Wherein, 100 is working electrode, and 150 is flexible back bone, and 200 is to electrode, and 300 is electroplate liquid, and 350 is reference electricity Pole, 400 is crucible, and 500 is fused salt, and 600 is flexible positive pole, and 650 is LiMn2O4.
Detailed description of the invention
The flexible carbon material related in the present invention, such as carbon nanometer paper, CNT, Buckie paper, carbon fiber, carbon felt, carbon cloth Or the fiber cloth of carbonization, they preparation methoies mainly have the pressing that bonds layer by layer, vacuum filtration, electrostatic spinning, overall acupuncture molding Etc..With specific reference to such as Publication about Document: material Leader (2010,24 (8), 13-17) to the preparation of carbon nanotube paper with study into The report of being reviewed property of exhibition.
The Master's thesis " preparation technology of hard carbon fiber entirety felt and performance study " of Dalian University of Technology then describes The technique that at present prepared by the carbon fibre material of main flow.
In the present invention, battery assembling electrolyte used is conventional LiPF6Base electrolyte, concrete formula is 1M LiPF6It is dissolved in Volume ratio is ethylene carbonate and the diethyl carbonate of 1:1.
Embodiment 1
Preparation of samples: by commercially-available flexible carbon nano tube thin film (CNT former state scanning electron microscope diagram such as Fig. 3 institute Show) it is positioned in tube furnace, under argon shield, it is heated to 1000 DEG C, heating rate is 10 DEG C/min, is incubated 2h, removes de-carbon The organic impurities of nanotube surface.Measure 4mL concentrated hydrochloric acid and 50mL deionized water, mix and blend, dilute salt of configuration 1mol/L Acid is standby, by W metal sheet (1 × 2cm2) and 1000 DEG C process after carbon nanotube paper (1 × 1cm2) respectively at dilute hydrochloric acid and third Ketone soaks 15min, then takes out, rinse well with deionized water, be positioned over drying for standby in 50 DEG C of baking ovens.
1) plating presoma
Compound concentration is that the aqueous solution of 0.01M manganese sulfate, 0.1M sodium sulfate and 0.1M sodium acetate is as electroplate liquid (300).With carbon Nano-tube film be working electrode (100), metal nickel sheet for being reference electrode (350) to electrode (200), silver/silver chloride, by electricity Pole is inserted and is carried out electrochemical deposition in electrolysis bath in electroplate liquid (300), and applying electric current density on the working electrode (s is 6.5 mA/ cm2Constant current, carry out electrochemical deposition, sedimentation time is 16 min, after having deposited, take out working electrode, make to spend Ionized water rinses electrode surface, remove be positioned in baking oven after soluble-salt be dried standby, intermediate product after plating step Scanning electron microscope diagram as shown in Figure 4.
2) prepared by fused salt
Weigh lithium nitrate and Lithium hydrate mixed grinding in mortar that mass ratio is 4:1.7, by dried working electrode (100) put into and take out after the fused salt of 300 DEG C carries out heat treated 60 min, clean with deionized water, put in Muffle furnace dry Dry rear standby, prepare flexible positive pole (600).
3) full battery assembling
Use commercialization to obtain graphited carbon nano-fiber as flexible negative pole, prepared flexible positive pole and flexible negative pole are pressed in Commercialization obtains battery diaphragm both sides, obtains carbon fiber surface felt as lug with commercialization, puts into flexible package bag, and packaging by hot pressing. Inject electrolyte from untight one end, more unencapsulated one end is carried out vacuum sealing.
Fig. 5 is after fused salt processes step, the scanning electron microscope diagram of positive electrode.Fig. 5 shows carbon nano tube flexible bone Frame (150) and the composite of LiMn2O4 (650), LiMn2O4 nanoscale twins well wraps CNT, forms one three Dimension network conformal structure, has preferable flex capability.
Fig. 6 is that after x-ray diffractometer scans fused salt process step in the range of 10 ~ 80 ° continuously, the XRD of positive electrode spreads out Penetrating collection of illustrative plates, it is consistent with LiMn2O4 characteristic peak, illustrates that the present invention has prepared LiMn2O4.
Fig. 7 is the chemical property result of flexible positive pole, is that lithium electrode carries out 500mA/g constant current charge-discharge test, The data of the charge and discharge cycles under 2.0V to 4.1V voltage window, show the electrochemical properties of layered lithium manganate, can obtain The full electrode specific capacity of 172.5 mAh/g.
Fig. 8 is the chemical property result of the flexible full battery of gained, is the 500mA/g constant current charge-discharge entering full battery Test, the data of the charge and discharge cycles under 2.0V to 4.1V voltage window.Can be seen that the electrification of the flexible full battery of acquisition Learn better performances.
Fig. 9 is the folding test result of the flexible full battery of gained, characterizes back and forth rolling over 0 ~ 180 ° of scope of full cell flexible The datagram of folded number of times and capability retention, by testing the folding of battery, finds that battery can sustain 3000 times past Multiple folding, shows high flex capability.
Embodiment 2
In the super flexible lithium ion of the present embodiment, the preparation of sample is similar to Example 1.First, carbon nano-tube film is positioned over Tube furnace is heated to 1000 DEG C of process, removes the Organic substance on surface, more just W metal sheet and the carbon nanotube paper after processing Soak in dilute hydrochloric acid and acetone respectively, be washed with deionized water clean, be positioned over drying for standby in 70 DEG C of baking ovens.
1) preparation plating presoma
Compound concentration is that the aqueous solution of 3 M manganese sulfates, 0.1 M sodium sulfate and 0.1 M sodium acetate is as electroplate liquid.With CNT Thin film be working electrode (100), metal nickel sheet for electrode (200) being carried out electrochemical deposition, apply permanent electricity on the working electrode (s Pressure carries out electrochemical deposition, and voltage can be the value in the middle of 0.75 ~ 1.4 V, and deposition typical time period is 5 min, has deposited it After, take out working electrode, use deionized water rinsing electrode surface, remove be positioned in baking oven after soluble-salt be dried standby With.Figure 10 is the scanning electron microscope (SEM) photograph of intermediate product after 1.4V electroplates.
2) prepared by fused salt
Weigh lithium nitrate and Lithium hydrate mixed grinding in mortar that mass ratio is 1:1, add 20wt% deionized water, allow profit Wet fused salt is put into together with electroplated sample in polytetrafluoroethyltank tank and is sealed, and is then heated to 180 DEG C, takes out, use after processing 6h Deionized water cleans, and puts in Muffle furnace the most standby, prepares flexible positive pole.Figure 11 is that 1.4V electrode fused salt processes step After, the scanning electron microscope (SEM) photograph of positive electrode.
3) prepared by full battery
Use graphited carbon nano-fiber as flexible negative pole, prepared flexible positive pole and flexible negative pole are pressed in battery diaphragm Both sides, with carbon fiber surface felt as lug, put into flexible package bag, and packaging by hot pressing.Electrolyte is injected from untight one end, Again unencapsulated one end is carried out vacuum sealing.
Figure 12 is that 1.4V sample is scanned in the range of 10 ~ 80 ° by x-ray diffractometer continuously, and XRD figure spectrum is special with LiMn2O4 Levy peak consistent, to illustrate that the present invention has prepared LiMn2O4.
The chemical property of described flexible positive pole is such as Figure 13, shown in 14, and Figure 13 is that fused salt processes after 0.75V constant voltage pulse After 500mA/g constant current charge-discharge test, 2.0V to 4.1V charge and discharge circulation data, show the electricity of layered lithium manganate Chemical property, can obtain the specific capacity of 156.5 mAh/g.Accompanying drawing 14 is the 500mA/ after fused salt processes after 1.4V constant voltage pulse G constant current charge-discharge is tested, the data that the heavily charge and discharge at 2.0V to 4.1V circulates, and shows the electrochemistry of layered lithium manganate Matter, can obtain the specific capacity of 152 mAh/g.The result of contrast Figure 13 and 14 shows, all can implement under other implementation conditions The result of example 1.
The folding of the flexible full battery of described 1.4V plating preparation is tested as shown in figure 15, and Figure 15 is that flexible battery capacity is protected Holdup and the relation of folding times, by testing the folding of battery, find that battery can sustain the reciprocal folding of 4000 times, Performance is except preferable flex capability.
Embodiment 3
In the super flexible lithium ion of the present embodiment, the preparation of sample is similar to embodiment 1,2.First, carbon nano-tube film is placed In tube furnace, it is heated to 1000 DEG C of process, removes the Organic substance on surface, more just W metal sheet and the CNT after processing Paper soaks respectively in dilute hydrochloric acid and acetone, is washed with deionized water clean, is positioned over drying for standby in 70 DEG C of baking ovens.
1) preparation plating presoma
Compound concentration is that the aqueous solution of 1 M manganese sulfate, 1 M sodium sulfate and 1 M sodium acetate is as electroplate liquid.
With carbon nano-tube film as working electrode, (100), metal nickel sheet are for electrode (200), silver/silver chloride being reference electricity Pole (350) carries out electrochemical deposition.It is 6.5 mA/cm in the upper electric current density that applies of working electrode (100)2Pulse constant current enter Row electrochemical deposition, the Exemplary deposition time is 11min.After having deposited, take out working electrode (100), use deionized water Rinse electrode surface, remove be positioned in baking oven after soluble-salt be dried standby.
2) prepared by fused salt:
Weigh lithium nitrate and Lithium hydrate mixed grinding in mortar that mass ratio is 4:1.7, add 10% deionized water.Will be dry Working electrode (100) after dry is put into after carrying out heat treated 60min in the fused salt of 200 DEG C and is taken out, and cleans with deionized water, puts Enter in Muffle furnace the most standby, prepare flexible positive pole.
3) prepared by full battery:
Use graphited carbon nano-fiber as flexible negative pole, prepared flexible positive pole and flexible negative pole are pressed in battery diaphragm Both sides, with carbon fiber surface felt as lug, put into flexible package bag, and packaging by hot pressing.Electrolyte is injected from untight one end, Again unencapsulated one end is carried out vacuum sealing.
After fused salt process step, the scanning electron microscope diagram of positive electrode, XRD figure are composed similar to Example 1, scanning electricity The flexible positive pole that the explanation of sub-microscope figure prepares is carbon nano tube flexible skeleton (150) and the composite of LiMn2O4 (650), manganese Acid lithium nanoscale twins well wraps CNT, forms a three-dimensional network conformal structure, has preferable flex capability. XRD figure spectrum display has prepared LiMn2O4.
The folding test result of the flexible full battery of gained is similar to Example 1.By the folding of battery is tested, find electricity Pond can sustain the reciprocal folding of 3000 times, and performance is except high flex capability.
Gained flexibility positive pole carries out lithium electrical testing, and electric discharge specific volume first is 125mAh/g, and efficiency first is 80%.Follow 83mAh/g is still had after ring 100 circle.
Embodiment 4
In the super flexible lithium ion of the present embodiment, the preparation of sample is similar to embodiment 1,2,3.First, carbon nano-tube film is put Be placed in tube furnace and be heated to 1000 DEG C of process, remove surface Organic substance, more just W metal sheet and process after carbon nanometer Pipe paper soaks respectively in dilute hydrochloric acid and acetone, is washed with deionized water clean, is positioned over drying for standby in 70 DEG C of baking ovens.
1) preparation plating presoma
Compound concentration is that the aqueous solution of 0.1 M manganese sulfate, 0.1 M sodium sulfate and 0.1 M sodium acetate is as electroplate liquid.
With carbon nano-tube film as working electrode, (100), metal nickel sheet are for electrode (200), silver/silver chloride being reference electricity Pole (350) carries out electrochemical deposition, carries out electrochemistry at the pulse constant voltage that working electrode (100) upper applying voltage is 1V and sinks Long-pending.The Exemplary deposition time is 10min；After having deposited, take out working electrode (100), use deionized water rinsing electrode table Face, remove be positioned in baking oven after soluble-salt be dried standby.
2) prepared by fused salt:
Weigh lithium nitrate and Lithium hydrate mixed grinding in mortar that mass ratio is 4:3, add the deionized water of 20wt%.Will Dried working electrode (100) is put into after carrying out heat treated 60min in the fused salt of 300 DEG C and is taken out, and cleans with deionized water, Put in Muffle furnace the most standby, prepare flexible positive pole.
3) prepared by full battery:
Use graphited carbon nano-fiber as flexible negative pole, prepared flexible positive pole and flexible negative pole are pressed in battery diaphragm Both sides, with carbon fiber surface felt as lug, put into flexible package bag, and packaging by hot pressing.Electrolyte is injected from untight one end, Again unencapsulated one end is carried out vacuum sealing.
After fused salt process step, the scanning electron microscope diagram of positive electrode, XRD figure are composed similar to Example 2, scanning electricity The flexible positive pole that the explanation of sub-microscope figure prepares is carbon nano tube flexible skeleton (150) and the composite of LiMn2O4 (650), manganese Acid lithium nanoscale twins well wraps CNT, forms a three-dimensional network conformal structure, has preferable flex capability. XRD figure spectrum display has prepared LiMn2O4.
The folding test result of the flexible full battery of gained is similar to Example 2.By the folding of battery is tested, find electricity Pond can sustain the reciprocal folding of 4000 times, and performance is except preferable flex capability.
Gained flexibility positive pole has been carried out lithium electric performance test, and first circle shows the specific capacity and 86% of 152mAh/g First circle efficiency.The specific capacity of 106mA/g is still had after circulating 100 times.

Claims (13)

1. a lithium ion battery flexibility positive pole, it is characterised in that described lithium ion battery flexibility positive pole is by lithium-ion electric The integration that pond positive-material lithium manganate (650) and flexible back bone (150) are formed solely stone electrode, described monolithic structure refers to electrode In various components intert and form an overall structure, rather than loosely, random stacking states.
Flexible positive pole the most according to claim 1, it is characterised in that in described flexible positive pole, lithium ion cell positive Material lithium manganate (650) conformal growth, on flexible back bone (150), described conformal refers to lithium cell anode material lithium manganate (650) the material morphology structure replication external surface shape of flexible back bone (150), uniformity on skeleton, form one The network of co-continuous, one of them continuous phase is active material, and another continuous phase is conductive flexible skeleton.
Flexible positive pole the most according to claim 1, it is characterised in that described lithium cell anode material lithium manganate (650) using electro-deposition and fused salt lithiumation two-step method to be prepared from, so-called flexible back bone (150) is selected from flexible carbon material.
Flexible positive pole the most according to claim 3, it is characterised in that described flexible carbon material is that carbon nanometer paper, carbon are received Mitron, Buckie paper, carbon fiber, carbon felt, carbon cloth or the fiber cloth of carbonization.
5. the preparation method of the flexible positive pole as described in claim 1-4 any one, it is characterised in that include following two steps:
1) select a kind of flexible back bone, use plating mode to deposit hydroxide oxygen manganese material on flexible back bone；
2) the hydroxide oxygen manganese material of electro-deposition lithiumation in the fused salt containing lithium salts of low melting point is processed, define conformal life Long lithium cell anode material lithium manganate on flexible back bone.
Preparation method the most according to claim 5, it is characterised in that the detailed process of described step 1) is as follows: select Working electrode (100), by working electrode (100) with electrode (200) is inserted into the electroplate liquid (300) containing divalent manganesetion In, electroplating process selects reference electrode (350), or only with containing working electrode (100) and two electrode body to electrode (200) System carries out electro-deposition, and electro-plating method uses constant current, constant voltage, cyclic voltammetric or pulse constant current constant voltage mode, deposition After completing, take out working electrode (100), rinse after electrode surface removes soluble-salt and be dried.
Preparation method the most according to claim 5, it is characterised in that described step 2) detailed process as follows:
1) by a certain proportion of lithium salt, put into and crucible (400) is heated to 180 ~ 300 ° of C, until melting completely, Then the dried working electrode (100) treating lithiumation is carried out lithiumation in being completely submerged in fused salt (500)；
2) after lithiumation has processed, being taken out by the working electrode of lithiumation, clean with deionized water, drying for standby, gained is soft Property positive pole (600).
8. according to the preparation method described in claim 6 or 7, it is characterised in that described working electrode (100) is selected from flexible carbon Material；Described is conductive material to electrode (200), selected from metal, graphite cake or material with carbon element.
Preparation method the most according to claim 8, it is characterised in that described material with carbon element be carbon nanometer paper, CNT, The fiber cloth of Buckie paper, carbon fiber, carbon felt, carbon cloth or carbonization.
Preparation method the most according to claim 6, it is characterised in that described electroplate liquid (300) includes containing 0.01 ~ 3M divalent manganesetion compound, also includes one or more in additive sodium sulfate, sodium acetate, ammonium acetate.
11. preparation methoies according to claim 7, it is characterised in that described fused salt include lithium nitrate, Lithium hydrate, One or more in lithium chloride.
12. preparation methoies according to claim 11, it is characterised in that described fused salt includes lithium nitrate and hydroxide Lithium, described lithium nitrate and Lithium hydrate mass ratio are 4:(1.7 4), wherein moisture is at 0 ~ 20wt%.
The 13. full batteries of super flexible lithium ion containing positive pole flexible as described in claim 1-4 any one, it is characterised in that Including sealing flexible package bag, being located at and seal the assembly that flexible package bag is internal, described assembly by the porous battery of centre every Film, be located at porous battery diaphragm side flexibility positive pole, be located at porous battery diaphragm other side flexible carbon nano tube negative pole or Person's graphited carbon fiber negative electrode layer is stacked, and is provided with electrolyte between described flexible package bag and assembly.
CN201610655022.0A 2016-08-10 2016-08-10 A kind of lithium ion battery flexibility positive pole, its preparation method and the super full battery of flexible lithium ion Pending CN106207091A (en)

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CN108232117A (en) * 2018-01-27 2018-06-29 浙江大学 A kind of lithium metal battery negative material and its preparation method and application
CN108923038A (en) * 2018-06-28 2018-11-30 宁波革创新材料科技有限公司 A kind of preparation method of environmental protection anode material of lithium battery
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CN109390549A (en) * 2018-10-17 2019-02-26 南通南京大学材料工程技术研究院 A kind of new preparation process of foldable lithium ion cell positive
CN109763263A (en) * 2019-01-31 2019-05-17 兰溪致德新能源材料有限公司 The technique that electrostatic spinning prepares silicon-carbon ear pole material
CN109763263B (en) * 2019-01-31 2021-03-09 兰溪致德新能源材料有限公司 Process for preparing silicon-carbon tab material by electrostatic spinning
CN110212156A (en) * 2019-05-31 2019-09-06 南方科技大学 Flexible electrode and preparation method and flexible lithium ion battery
CN112938927A (en) * 2021-05-12 2021-06-11 蜂巢能源科技有限公司 Preparation method of lithium iron phosphate
CN114583179A (en) * 2022-03-04 2022-06-03 远景动力技术(江苏)有限公司 Flexible lithium ion battery and manufacturing method thereof

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