CN109390549A - A kind of new preparation process of foldable lithium ion cell positive - Google Patents

A kind of new preparation process of foldable lithium ion cell positive Download PDF

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Publication number
CN109390549A
CN109390549A CN201811206200.7A CN201811206200A CN109390549A CN 109390549 A CN109390549 A CN 109390549A CN 201811206200 A CN201811206200 A CN 201811206200A CN 109390549 A CN109390549 A CN 109390549A
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lithium
foldable
manganese
lithium ion
manganese oxide
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濮军
王建
沈子涵
张会刚
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Nantong nanjing university material engineering technology research institute
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Nantong nanjing university material engineering technology research institute
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 present invention provides a kind of new processes of foldable lithium ion cell positive.The anode (600) of this folding lithium ion full battery is to react the integrated conformal electrode formed by LiMn2O4 shell (650) and bent carbon nanotube skeleton (150).The preparation method of foldable lithium ion cell positive includes following two steps: (1) using the hydroxyl manganese oxide layer of water phase electrically-driven ion oxidizing process depositing homogeneous in foldable flexible substrate；(2) using melting lithiumation process, in the molten system that hydroxyl manganese oxide presoma is put into lithium-containing compound under low temperature, lithiumation is lithium cell anode material lithium manganate.What the present invention can achieve has the technical effect that, without extra binder and conductive agent, the foldable conformal cathode film of LiMn2O4 has good mechanical strength and flexibility, and entire electrode can receive significantly deformation during bending.

Description

A kind of new preparation process of foldable lithium ion cell positive
Technical field
The invention belongs to electrochemical energy storage fields, and in particular to a kind of folding lithium ion cell positive preparation process.
Background technique
With the progress of intelligence science and technology, various flexible apparatus also become the main force of electronic market.Current flexibility Equipment mainly flexible display, radio-frequency card, the wearable product of intelligence and sensor etc..But folding lithium battery technology It develops slowly, becomes a restraining factors of high-end flexible electronic equipment development.Existing conventional batteries all have rigid mostly Property and thickness in terms of the shortcomings that, limit its it is wearable with bending field of electronic device in use.So being badly in need of developing A kind of folding lithium ion battery.
In general, mainly by electrode, electrolyte, diaphragm and shell, these constituent elements are constituted lithium battery, wherein foldable electricity The preparation research and development of pole are then the key points of entire foldable battery.And positive (cathode) material of current business, mainly cobalt Sour lithium, LiMn2O4, LiFePO 4 (graphite, lithium titanate) etc..Traditional preparation process is all by positive (cathode) material and to lead The additives such as electric agent (acetylene black, Ketjen black, Super P etc.), binder (polyvinylidene fluoride, polytetrafluoroethylene (PTFE) etc.), thickener are mixed It closes stirring and forms slurry, and by slurry coating on two-dimensional metal aluminum foil or copper foil, after electrode slice is made, the gold of additional tempering Belong to shell, formation can not folding lithium ion battery.
Currently, researcher is the battery case using non-tempering and the collector that can be bent mostly to prepare The positive and negative anodes of electrode, there are two types of the specific forms of expression: being coated on conductive agent, binder and positive electrode one is traditional On folding collector (such as thin layer aluminium foil, graphene film, Buckie paper), mechanical performance is still to be connected by using binder Collector is connect with active material to be promoted；Another kind is the self-supporting system using binder free, it is general using filter film forming or The methods of solvent evaporation film forming, is embedded in folding conductive current collector (such as three-dimensional grapheme for the positive electrode of rigidity at random Film, carbon nano-tube film etc.) in.Although these methods improve the foldability energy of electrode to a certain extent, at this In a little methods, positive electrode still passes through the micron particles that 700-1000 DEG C of high temperature sintering obtains, with folding substrate Contact be the later period physical contact.In prolonged bending process, these positive electrodes can not in deformation with can roll over Folded collector keeps good contact, reduces the utilization rate of active material, while the stress of particle can not shift, easily The problems such as active material removing occur and falling off leads to electrode slice breakage, pierces through situations such as diaphragm, make battery failure.To not It is able to satisfy the needs of foldable electronic.
Therefore, how to be prepared into positive electrode active materials are in situ on folding collector, it is conformal to form co-continuous Anode is the research emphasis of foldable lithium battery development at present.
Based on existing lithium ion battery feature, the invention proposes a kind of foldable electrode anode with low energy consumption New preparation process further improves the foldability energy and chemical property of lithium ion battery, wearable energy storage has been pushed to set It is standby horizontal to further increase and develop.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of foldable lithium ion cell positive to solve to pass Battery unite at the foldable aspect the drawbacks of, to meet the growth requirement of the following wearable device, meanwhile, providing a kind of has low consumption The low temperature preparation method of energy prepares positive-material lithium manganate, energy saving.
Mentality of designing in the present invention for foldable positive (600) of lithium ion battery is by using a kind of foldable Carbon nanotube paper skeleton (150) accept stress, by by method on positive lithium manganate material growth in situ to the skeleton A kind of composite construction is formed, this combination electrode has folding kernel conducting matrix grain (150) and can be used as the mangaic acid of anode The continuous shell of lithium (650) is a kind of whole core-shell structure that nanoscale range class is conformal, rather than mangaic acid loosely, at random Lithium particle packing state.In prolonged bending process, shell is by stress transfer to soft kernel, and deformation occurs.It is real On border, the relative displacement of minimum degree only has occurred between shell and inner skeleton, to maintain electronic conduction, maintains higher Battery performance.
Present invention process process is as shown in Figure 1, include following concrete operation step:
(1) conformal uniform on foldable flexible substrate carbon nanotube skeleton (150) using water phase electrically-driven ion oxidizing process Deposit hydroxyl manganese oxide layer.
(2) using melting lithiumation process, hydroxyl manganese oxide presoma is put into the melting of lithium-containing compound under low temperature In system, lithiumation is lithium cell anode material lithium manganate shell (650).
Detailed process is as follows for the step (1): by carbon nanotube paper skeleton (150), reference electrode (350) and to electricity Pole (200) is inserted into the aqueous solution containing divalent manganesetion (300), apply constant current or constant voltage carry out electric drive from Sub- oxidizing process operation.After deposition is completed, take out carbon nanotube paper skeleton (150), after washing, 60 DEG C of dryings of vacuum.
Optimization, the reference electrode in the step (1), can for saturated calomel electrode, silver/silver chloride electrode and mercury/ One of mercuric oxide electrode.
Optimization, in the step (1) to electrode, can be one of metallic nickel, platinum and graphite plate.
Optimization, the aqueous solution as described in step (1) be divalent manganese ion compound, manganese sulfate, manganese acetate, One of manganese chloride additionally needs that one or more of sodium sulphate, sodium acetate, potassium acetate additive is added.
Optimization, the concentration of divalent manganesetion described in the step (1) is 0.1-3 mol/L, and the concentration of additive is 0.1-1 mol/L.
Optimization, water phase electrically-driven ion oxidizing process prepares hydroxyl manganese oxide in the step (1), which is characterized in that permanent The range of electric current is 2-7 mA/cm2Or the range of constant voltage is 0.75-1.4 V, bivalent manganese is manganic by electroxidation, and It is deposited on displacement to carbon nanotube skeleton (150).
Detailed process is as follows for the step (2): by a certain proportion of lithium-containing compound mixed grinding, being put into crucible (400) it is heated to 180-300 DEG C in, until melting completely, then receives the hydroxyl manganese oxide carbon coated to lithiumation after drying Mitron skeleton composite construction, which is completely submerged in the lithium-containing compound (500) of melting, carries out lithiumation.It, will after lithiumation processing is completed The electrode of lithiumation takes out, and is cleaned with deionized water, drying for standby, and gained is foldable positive (600).
Optimization, the melting lithium-containing compound in the step (2) includes in lithium hydroxide and lithium nitrate, lithium chloride One or two, mass ratio are (1.7-4): 4, moisture content is in 0-20wt%.
Optimization, low temperature refers between 180-300 DEG C in the step (2).
Compared with prior art, the present invention has the following technical effect that
1, the pottery conformal with carbon nanotube skeleton kernel has been prepared in situ on carbon nanotube skeleton collector (150) in the present invention The lithium manganate cathode (as shown in Figure 2) of porcelain phase.Different from prepared by conventional coating process electrode (it is relatively crisp, after bending Active layer can be caused to fall off), the characteristics of this preparation process in situ, ensure that the attachment of electrode material on a current collector more It is close firm, during folding, although deformation has occurred in entire combination electrode, in inside battery anode ceramic material Stress is forwarded to flexible back bone, skeleton receives deformation, avoids the brittle failure of positive electrode.
2, the invention proposes a kind of low temperatures, low consumed manganate cathode material for lithium preparation means.Conventional high-temperature solid phase Synthetic lithium manganate, temperature can have very high temperature, huge energy consumption between 700 DEG C to 1000 DEG C.The present invention melts lithiumation method Temperature substantially reduced compared to traditional technology, effectively reduce energy loss.Meanwhile the tune relative to high temperature process heat method It is single to control parameter, the present invention has wider parameter modification scope.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram of the lithium ion cell positive that can be folded time of the invention.
Fig. 2 is the present invention with conformal schematic diagram shown in carbon nanotube skeleton.
Fig. 3 is carbon nanotube skeleton original sample scanning electron microscope diagram piece.
Fig. 4 is the scanning electron microscope diagram piece of hydroxyl manganese oxide enveloped carbon nanometer tube skeleton in embodiment 1.
Fig. 5 is to complete after melting lithiumation processing, positive scanning electron microscope diagram in embodiment 1.
Fig. 6 is the XRD diffracting spectrum of prepared manganate cathode material for lithium in embodiment 1.
Fig. 7 is charge-discharge test curve of the prepared half-cell under 500 mA/g constant current densities in embodiment 1.
Fig. 8 is charge-discharge test curve of the prepared full battery under 500 mA/g constant current densities in embodiment 1.
Fig. 9 is data of the folding full battery in 0-180 ° of reciprocal folding times and capacity retention ratio in embodiment 1 Figure.
Figure 10 is the scanning electron microscope diagram piece of hydroxyl manganese oxide enveloped carbon nanometer tube skeleton in embodiment 2.
Figure 11 is to complete after melting lithiumation processing, positive scanning electron microscope diagram in embodiment 2.
Figure 12 is the XRD diffracting spectrum of prepared manganate cathode material for lithium in embodiment 2.
Figure 13 is charge-discharge test curve of the prepared half-cell under 500 mA/g constant current densities in embodiment 2.
Figure 14 is charge-discharge test curve of the prepared full battery under 500 mA/g constant current densities in embodiment 2.
Figure 15 is data of the folding full battery in 0-180 ° of reciprocal folding times and capacity retention ratio in embodiment 2 Figure.
Wherein, (150) are carbon nanotube scaffold base, and (200) are to electrode, and (300) are water system divalent manganese solution, It (350) is reference electrode, (400) are crucible, and (500) lithium-containing compound fusant, (600) are folding anode, and (650) are LiMn2O4 shell.
Specific embodiment
A specific embodiment of the invention is illustrated below with reference to reference attached drawing and example.It is to be noted that the present invention is contained Temperature range, the battery system range of lid are not only limited to these embodiments.Selected carbon nanotube skeleton such as Fig. 3 institute Show, diameter is about 50 nm.
Embodiment 1
This example is that specific preparation process is as follows:
(1) configuration concentration is the water-soluble of the manganese sulfate of 0.1 mol/L, 0.1 mol/L sodium sulphate and 0.1 mol/L sodium acetate Liquid uses metal nickel sheet for electrode (200), silver/silver chloride electrode is reference electrode as water system divalent manganese solution (300) (350), applying current density is 6.5 mA/cm2Constant current, carry out electrically-driven ion oxidation operation, the operating time be 16 points Clock, after deposition is completed, takes out carbon nanotube electrode, rinses electrode surface using deionized water, places after removing soluble-salt It is dried in baking oven spare, scanning electron microscope diagram is as shown in Figure 4.
(2) lithium nitrate and the lithium hydroxide mixed grinding in mortar that mass ratio is 4:1.7 are weighed, is heated to 300 DEG C, to It melts, and hydroxyl manganese oxide enveloped carbon nanometer tube skeleton after drying is put into progress lithiumation processing in above-mentioned system and is taken after sixty minutes Out, it is cleaned with deionized water, is put into spare after drying in Muffle furnace, obtained flexible anode (600).
Fig. 5 is the scanning electron microscope diagram of positive electrode after melting lithiumation processing.As can be seen from Figure 5 LiMn2O4 Nanoscale twins are wrapped in carbon nanotube skeleton well, form a three-dimensional network conformal structure.
Fig. 6 is that XRD's x-ray diffractometer of positive electrode spreads out after continuous scanning melting lithiumation processing within the scope of 10-80 ° Map is penetrated, it is consistent with LiMn2O4 characteristic peak, illustrate lithium manganate material produced by the present invention.
Fig. 7 be in embodiment 1 lithium manganate cathode to lithium cathode sheet preparation half-cell chemical property as a result, its In, electrolyte is 1 mol/L LiPF6It is dissolved in the ethylene carbonate and diethyl carbonate that volume ratio is 1:1.It is close to test electric current Degree is 500 mA/g, and voltage window is 2.0-4.1 V, it can be seen from figure 7 that the half-cell shows the electricity of layered lithium manganate Chemical property can obtain the specific capacity of 172.5mAh/g.
Fig. 8 is in embodiment 1, using the carbon nano-tube film of prelithiation as the chemical property knot of the foldable full battery of cathode Fruit, electrolyte are 1 mol/L LiPF6It is dissolved in the ethylene carbonate and diethyl carbonate that volume ratio is 1:1.It is close to test electric current Degree is 500 mA/g, and voltage window is 2.0-4.1 V, the electrochemical performance of the full battery as can be seen from the figure obtained.
Fig. 9 be in embodiment 1 the foldable full battery of gained in the reciprocal folding times of 0-180 ° of range and capacity retention ratio Datagram.By folding to battery test, discovery battery can sustain 3000 times reciprocal and fold that (capacity is maintained at 62% More than), show high prolonged folding property.
Embodiment 2
This example is that specific preparation process is as follows:
(1) configuration concentration is the aqueous solution of the manganese sulfate of 3 mol/Ls, 0.1 mol/L sodium sulphate and 0.1 mol/L sodium acetate As water system divalent manganese solution (300), use Pt metal piece for electrode (200), silver/silver chloride electrode is reference electrode (350), it is applied for the constant voltage of 1.4 V, carries out electrically-driven ion oxidation operation, the operating time is 6 minutes, deposition completion Afterwards, carbon nanotube electrode is taken out, electrode surface is rinsed using deionized water, is placed in baking oven and is done after removing soluble-salt Dry spare, scanning electron microscope diagram is as shown in Figure 10.
(2) lithium nitrate and the lithium hydroxide mixed grinding in mortar that mass ratio is 1:1 are weighed, is added after being heated to 180 DEG C The deionized water for entering 20wt%, to its thawing, by hydroxyl manganese oxide enveloped carbon nanometer tube skeleton after drying be put into above-mentioned system into The processing of row lithiumation is taken out after sixty minutes, is cleaned with deionized water, and spare after drying in Muffle furnace, obtained flexible anode is put into (600).
Figure 11 is the scanning electron microscope diagram of positive electrode after melting lithiumation processing.As can be seen from Figure 11 mangaic acid Lithium nanoscale twins are wrapped in carbon nanotube skeleton well, form a three-dimensional network conformal structure.
Figure 12 is the XRD spectrum of positive electrode after the processing of melting lithiumation in embodiment 2, opposite with the characteristic peak of LiMn2O4 It answers, has illustrated lithium manganate material produced by the present invention.
Figure 13 be in embodiment 2 lithium manganate cathode to lithium cathode sheet preparation half-cell chemical property as a result, its In, electrolyte is similar to Example 1, is 1 mol/L LiPF6It is dissolved in the ethylene carbonate and carbonic acid diethyl that volume ratio is 1:1 Ester.Test current density is 500 mA/g, and voltage window is 2.0-4.1 V, it can be observed from fig. 13 that the half-cell is shown Typical layered lithium manganate electrochemistry charge and discharge curve, can obtain the specific capacity of about 155 mAh/g.
Figure 14 is the foldable full electricity assembled by anode prepared by cathode and embodiment 2 of the carbon nano-tube film of prelithiation The chemical property in pond is as a result, electrolyte is 1 mol/L LiPF6It is dissolved in the ethylene carbonate and carbonic acid two that volume ratio is 1:1 Ethyl ester.Test current density is 500 mA/g, and voltage window is 2.0-4.1 V, the full battery as can be seen from the figure obtained Electrochemical performance is about 151 mAh/g.
Figure 15 is number of the 2 foldable full battery of gained of embodiment in 0-180 ° of range reciprocal folding times and capacity retention ratio According to figure.By the folding test to battery, discovery battery can sustain 4000 reciprocal foldings, show high length The folding property of time.

Claims (8)

1. a kind of new process of foldable lithium ion cell positive, which comprises the steps of:
(1) the uniform deposition hydroxyl manganese oxide layer conformal in foldable flexible substrate using water phase electrically-driven ion oxidizing process；
(2) using melting lithiumation process, hydroxyl manganese oxide presoma is put into the molten system of lithium-containing compound under low temperature In, lithiumation is lithium cell anode material lithium manganate.
2. the new process of foldable lithium ion cell positive according to claim 1, which is characterized in that foldable in electrode Active material LiMn2O4 mutually one continuous overall structure of interspersed formation in substrate, rather than LiMn2O4 loosely, at random Particle packing state.
3. water phase electrically-driven ion oxidizing process according to claim 1 prepares hydroxyl manganese oxide, which is characterized in that described Detailed process is as follows for step (1): being inserted into carbon nanotube paper skeleton (150), reference electrode (350) and to electrode (200) In aqueous solution (300) containing divalent manganesetion, applies constant current or constant voltage carries out the operation of electrically-driven ion oxidizing process；
After deposition is completed, take out carbon nanotube paper skeleton (150), after washing, 60 DEG C of dryings of vacuum.
4. water phase electrically-driven ion oxidizing process according to claim 3 prepares hydroxyl manganese oxide, which is characterized in that described Aqueous solution be divalent manganese ion compound, one of manganese sulfate, manganese acetate, manganese chloride, additionally need be added sodium sulphate, One or more of sodium acetate, potassium acetate additive.
5. the aqueous solution of the manganese ion compound of divalent according to claim 4, which is characterized in that the bivalent manganese from The concentration of son is 0.1-3 mol/L, and the concentration of additive is 0.1-1 mol/L.
6. water phase electrically-driven ion oxidizing process according to claim 3 prepares hydroxyl manganese oxide, which is characterized in that constant current Range be 2-7 mA/cm2Or the range of constant voltage is 0.75-1.4 V.
7. the new process of foldable lithium ion cell positive according to claim 1, which is characterized in that the melting contains Lithium compound includes one or both of lithium hydroxide and lithium nitrate, lithium chloride, and mass ratio is (1.7-4): 4, moisture Content is in 0-20wt%.
8. the new process of foldable lithium ion cell positive according to claim 1, which is characterized in that the low temperature is Refer between 180-300 DEG C.
CN201811206200.7A 2018-10-17 2018-10-17 A kind of new preparation process of foldable lithium ion cell positive Pending CN109390549A (en)

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Publication number Priority date Publication date Assignee Title
CN114566392A (en) * 2022-03-18 2022-05-31 南昌航空大学 Oxygen-enriched defect epsilon-MnO2Preparation method of/carbon quantum dot composite film
CN114566392B (en) * 2022-03-18 2023-04-11 南昌航空大学 Oxygen-enriched defect epsilon-MnO 2 Preparation method of/carbon quantum dot composite film

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Application publication date: 20190226