CN104538581A - Three-dimensional porous lithium manganate film electrode and preparing method and application thereof - Google Patents
Three-dimensional porous lithium manganate film electrode and preparing method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a three-dimensional porous lithium manganate film electrode, a preparing method of the three-dimensional porous lithium manganate film electrode and the application of the three-dimensional porous lithium manganate film electrode as the positive pole of a lithium ion battery. The preparing method includes the steps that a high-molecular polymer porous film with a hydrophilic surface is obtained through pretreatment; the chemical bath deposition method is used for depositing manganese oxide to the surface of the high-molecular polymer porous film with the hydrophilic surface so as to obtain a precursor film containing manganese; the precursor film containing manganese is soaked into a solution containing lithium, and the mixed solution reacts in the protective atmosphere for 0.5-8 h at the temperature of 250 DEG C-400 DEG C and then reacts in the air atmosphere for 1-10 h at the temperature of 500 DEG C-900 DEG C to obtain the three-dimensional porous lithium manganate film electrode finally. The three-dimensional porous lithium manganate film electrode is an overall electrode, does not need addition of an adhesion agent or a conductive agent, has excellent rate performance and cycling stability and can be widely applied to the fields of high-performance lithium ion batteries and the like as the positive pole of the lithium ion battery.
Description
Technical field
The present invention relates to lithium ion cell positive field, be specifically related to a kind of three-dimensional porous LiMn2O4 membrane electrode and preparation method thereof and the application as lithium ion cell positive.
Background technology
LiMn
2o
4its Stability Analysis of Structures is good, and security performance is strong, has higher theoretical capacity (148mAh/g) and discharge voltage (4.15V).In addition, promoter manganese enriches, cheap, nontoxic, therefore, and LiMn
2o
4as positive electrode, there is great potentiality and attraction.But there is the problem of following three aspects in actual applications in this type of material.First, LiMn
2o
4carry out at 3.3-4.3V voltage range that lithium ion is embedding/de-can cause LiMn
2o
4the violent expansion/contraction of crystal structure generation asymmetry (i.e. Jahn-Teller effect), occurs that serious cycle life declines.Secondly, due to Mn
3+there is disproportionated reaction and can generate Mn
2+ion is also dissolved in electrolyte, therefore LiMn
2o
4crystal structure can suffer irreversible breaking, causes capacity significantly to be decayed.3rd, under the high temperature conditions with under overcharge conditions, electrolyte oxidation all can be caused to decompose, thus affect LiMn
2o
4chemical property and fail safe.These problems seriously constrain the commercial applications of manganese monoxide as positive electrode.
Current synthesis LiMn
2o
4the method of material mainly concentrates on high temperature solid phase synthesis, hydrothermal synthesis method, melt impregnation, sol-gal process and coprecipitation etc.The people such as Wan (Wan C Y, et al.Synthesis of spinel LiMn
2o
4using direct solid state reaction [J] .Materials Letters, 2002,56 (3): 357-363.) utilize the manganese dioxide of electrosynthesis glyoxal for manganese source, the lithium manganate material first discharge specific capacity of being synthesized by high temperature solid-state method is close to 120mAh g
-1, and the capability retention after 80 circulations is higher than 85%.The people such as Kim (Kim D K, et al.Spinel LiMn
2o
4nanorods as lithiumion battery cathodes [J] .Nano Letters, 2008,8 (11): 3948-3952.) adopt monocrystalline β-MnO
2nanometer rods is raw material, and in conjunction with hydro thermal method synthetic single crystal LiMn2O4 nano wire, under 1C multiplying power, specific discharge capacity is higher than 100mAh g
-1.The people such as Liu Qiaosheng (Liu Qiaosheng etc. sol-gel process synthesis of anode material of lithium-ion battery LiMn
2o
4[J]. New Chemical Materials, 2010,38 (2): 90-92.) with manganese acetate and lithium nitrate for raw material, ethylenediamine tetra-acetic acid-citric acid is that complexing agent obtains LiMn
2o
4, under 0.5C multiplying power, specific discharge capacity can reach 120mAh g
-1.The people such as He Xiangming (He Xiangming etc. based on the lithium ion battery anode material spherical LiMn2O4 [J] that crystallization control legal system is standby. China YouSe Acta Metallurgica Sinica, 2005,15 (9): 1390-1395.) the spherical lithium manganate powder utilizing coprecipitation to prepare has high-tap density and excellent chemical property.
Although relevant LiMn at present
2o
4the preparation research of material has obtained certain progress, but prepares high-quality LiMn
2o
4material is powder body material, and complex process, cost is higher, is unfavorable for suitability for industrialized production and electrode preparation.In addition, the Method and process of regarding three-dimensional porous LiMn2O4 membrane electrode one-step synthesis, both at home and abroad there are no report.
Summary of the invention
First object of the present invention be to provide a kind of low cost, be applicable to the three-dimensional porous LiMn2O4 membrane electrode without the need to binding agent and conductive agent of suitability for industrialized production.
Second object of the present invention is that described three-dimensional porous LiMn2O4 membrane electrode is used as lithium ion cell positive.
Below technical scheme of the present invention is illustrated.
A preparation method for three-dimensional porous LiMn2O4 membrane electrode, comprises the following steps:
1) preliminary treatment of high molecular polymer perforated membrane: high molecular polymer perforated membrane is immersed in strong oxidizing property acid solution, hydrophilicity-imparting treatment 0.5-24 hour under 40-80 DEG C of condition, washing, to neutral, obtains the high molecular polymer perforated membrane of surface hydrophilic;
2) prepare the mixed solution that be made up of potassium permanganate, sodium sulphate and water as chemical plating fluid, adopt chemical bath deposition method, by the high molecular polymer porous film surface of manganese-oxide deposition at surface hydrophilic, obtain containing manganese precursor thin-film;
3) will be impregnated in lithium-containing solution containing manganese precursor thin-film, in 250-400 DEG C of reaction 0.5-8 hour under protective atmosphere, more in air atmosphere in 500-900 DEG C of reaction 1-10 hour, finally obtain three-dimensional porous LiMn2O4 membrane electrode.
Step 1) in, described high molecular polymer perforated membrane is preferably polypropylene screen, polyethylene film or polypropylene, polyethylene composite wood plasma membrane, and thickness is less than 50 μm, is generally greater than 100nm.High molecular polymer perforated membrane can adopt prior art, adopts commercially available prod or adopts existing method to prepare.
Step 1) in, described strong oxidizing property acid solution is preferably at least one in hydrochloric acid solution (i.e. hydrochloric acid), salpeter solution (i.e. nitric acid), sulfuric acid solution (i.e. sulfuric acid) (i.e. one or more), further preferably, described strong oxidizing property acid solution is preferably at least two kinds in hydrochloric acid solution, salpeter solution, sulfuric acid solution, namely adopts the mix acid liquor of any two or more than two kinds.
Step 2) in, the mixed solution be made up of potassium permanganate, sodium sulphate and water is chemical plating fluid, in described chemical plating fluid, the mol ratio of potassium permanganate and sodium sulphate is preferably 1:0.8 ~ 1.2, and in described chemical plating fluid, the total concentration of potassium permanganate and sodium sulphate is 0.01-1mol/L.
Chemical bath deposition method of the present invention is specific as follows: the high molecular polymer perforated membrane of surface hydrophilic is immersed chemical plating fluid, soaks after 0.5-1 hour, be separated by high molecular polymer perforated membrane with solution, namely obtains containing manganese precursor thin-film after washing, drying.
Step 3) in, described lithium-containing solution is the solution that can provide elemental lithium, solvent can be deionized water or ethanol etc., as lithium hydroxide aqueous solution, water lithium chloride solution, the lithium acetate aqueous solution, the lithium nitrate aqueous solution, the lithium sulfate aqueous solution or lithium carbonate ethanolic solution etc., namely described lithium-containing solution is at least one in lithium hydroxide aqueous solution, water lithium chloride solution, the lithium acetate aqueous solution, the lithium nitrate aqueous solution, the lithium sulfate aqueous solution, lithium carbonate ethanolic solution.The concentration of described lithium-containing solution is not more than 0.1g/mL, i.e. 0.001 ~ 0.1g/mL.Protective atmosphere of the present invention refers under the conditions of the reaction according to the invention, the gas of not having an effect with reaction system, therefore it not only refers to the inert gas on ordinary meaning, the preferred argon gas of protective atmosphere of the present invention or nitrogen.
To be impregnated in lithium-containing solution containing manganese precursor thin-film; in 300 DEG C of reactions 2 hours under protective atmosphere; again in air atmosphere in 800 DEG C of reactions 8 hours; finally obtain three-dimensional porous LiMn2O4 membrane electrode; above-mentioned specified temp and special time can have an impact to the pattern of three-dimensional porous LiMn2O4 membrane electrode, make it have excellent electric property.
Three-dimensional porous LiMn2O4 membrane electrode prepared by the present invention is a kind of overall electrode, and it is without the need to adding binding agent and conductive agent.
Present invention also offers the application of described three-dimensional porous LiMn2O4 membrane electrode as lithium ion cell positive.
Compared with prior art, beneficial effect of the present invention is:
One, the present invention takes full advantage of the high molecular polymer perforated membrane of low cost as the direct synthetic lithium manganate membrane electrode of template, and without the need to subsequent electrode preparation process, adds binding agent and conductive agent.The method is simple, with low cost, easily realizes industrialization.
Two, the three-dimensional porous LiMn2O4 membrane electrode that the present invention obtains has three-D space structure, and porous character, not only can improve the specific area of lithium manganate material, increase electrochemical reaction area, obtain high rate capability, the dry linting problem of Cracking that simultaneously can effectively prevent Powder electrode common, strengthens its cycle performance and fail safe.Therefore, the three-dimensional porous LiMn2O4 membrane electrode of gained has excellent high rate performance and cyclical stability, can be used as lithium ion cell positive and is widely used in the fields such as high performance lithium ion battery.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 obtain three-dimensional porous LiMn2O4 membrane electrode XRD figure;
Fig. 2 is the cycle performance curve chart of the simulated battery prepared by embodiment 1.
Embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
Embodiment 1
1) in the embodiment of the present invention, the preliminary treatment of high molecular polymer perforated membrane adopts following steps: take deionized water as solvent preparation 500mL strong oxidizing property acid solution, it is 1:1 mixing by the mol ratio of hydrochloric acid and sulfuric acid, then deionized water is added to 500mL, obtain 500mL strong oxidizing property acid solution, wherein the gross mass percentage of hydrochloric acid and sulfuric acid is 15%.High molecular polymer perforated membrane (polyethylene porous matter film, day east SUNMAP) is immersed in this strong oxidizing property acid solution, hydrophilicity-imparting treatment 6 hours at 60 DEG C.Adopt deionized water by the washing of high molecular polymer perforated membrane to neutral, the high molecular polymer perforated membrane of acquisition surface hydrophilic.
2) 1.58g potassium permanganate and 1.42g sodium sulphate are dispersed in 50mL deionized water, obtain chemical bath deposition reactant liquor (i.e. chemical plating fluid).Be impregnated in above-mentioned chemical bath deposition reactant liquor by the high molecular polymer perforated membrane of surface hydrophilic again, the chemical bath deposition time is 1 hour.Then high molecular polymer perforated membrane is separated with solution, with deionized water cyclic washing for several times, being placed in temperature is that the baking oven of 80 DEG C is dried, obtains containing manganese precursor thin-film.
3) get the dried manganese precursor thin-film that contains of 0.1g and be placed in crucible; add 5mL containing 0.01g/mL lithium hydroxide aqueous solution; then crucible is placed in the reacting furnace that temperature is 300 DEG C, pass into flow be the nitrogen of 200sccm as protective gas, react 2 hours.Finally obtain end product in 800 DEG C of calcinings after 8 hours in air atmosphere, be three-dimensional porous LiMn2O4 membrane electrode.
Fig. 1 is the XRD diffraction pattern of this three-dimensional porous LiMn2O4 membrane electrode, and reference standard card is known, and products therefrom is LiMn
2o
4, exist without other impurity.
Lithium ion battery is made as follows with the three-dimensional porous LiMn2O4 membrane electrode of embodiment 1 gained.
With three-dimensional porous LiMn2O4 membrane electrode for positive pole, metal lithium sheet is negative pole, and electrolyte is 1mol/LLiPF
6/ EC-DMC (volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard 2300), is assembled into simulated battery.Fig. 2 is the cyclic curve of respective battery under 0.5C current density in 3.0-4.5V voltage range, can find that this thin-film electrode material has excellent cyclical stability, and after 50 circulations, specific capacity is still higher than 100mAh g
-1.
Embodiment 2
1) in the embodiment of the present invention, the preliminary treatment of high molecular polymer perforated membrane adopts following steps: take deionized water as solvent preparation 500mL strong oxidizing property acid solution, it is 1:1 mixing by the mol ratio of hydrochloric acid and sulfuric acid, then deionized water is added to 500mL, obtain 500mL strong oxidizing property acid solution, wherein the gross mass percentage of hydrochloric acid and sulfuric acid is 15%.High molecular polymer perforated membrane (polyethylene porous matter film, day east SUNMAP) is immersed in this strong oxidizing property acid solution, hydrophilicity-imparting treatment 6 hours at 60 DEG C.Adopt deionized water by the washing of high molecular polymer perforated membrane to neutral, the high molecular polymer perforated membrane of acquisition surface hydrophilic.
2) 1.58g potassium permanganate and 1.42g sodium sulphate are dispersed in 50mL deionized water, obtain chemical bath deposition reactant liquor (i.e. chemical plating fluid).Be impregnated in above-mentioned chemical bath deposition reactant liquor by the high molecular polymer perforated membrane of surface hydrophilic again, the chemical bath deposition time is 1 hour.Then high molecular polymer perforated membrane is separated with solution, with deionized water cyclic washing for several times, being placed in temperature is that the baking oven of 80 DEG C is dried, obtains containing manganese precursor thin-film.
3) get the dried manganese precursor thin-film that contains of 0.1g and be placed in crucible; add 5mL containing 0.01g/mL lithium hydroxide aqueous solution; then crucible is placed in the reacting furnace that temperature is 400 DEG C, pass into flow be the nitrogen of 200sccm as protective gas, react 2 hours.Finally obtain end product in 600 DEG C of calcinings after 8 hours in air atmosphere, be three-dimensional porous LiMn2O4 membrane electrode.
Embodiment 2 first adopts 400 DEG C of reactions, then 600 DEG C of calcinings, other conditions are with embodiment 1.With the method assembling simulated battery of obtained three-dimensional porous LiMn2O4 membrane electrode by embodiment 1, test.Can find that this thin-film electrode material has excellent cyclical stability, after 50 circulations, specific capacity is 90mAh g
-1.
Embodiment 3
1) in the embodiment of the present invention, the preliminary treatment of high molecular polymer perforated membrane adopts following steps: take deionized water as solvent preparation 500mL strong oxidizing property acid solution, it is 1:1 mixing by the mol ratio of hydrochloric acid and nitric acid, then deionized water is added to 500mL, obtain 500mL strong oxidizing property acid solution, wherein the gross mass percentage of hydrochloric acid and nitric acid is 15%.High molecular polymer perforated membrane (polyethylene porous matter film, day east SUNMAP) is immersed in this strong oxidizing property acid solution, hydrophilicity-imparting treatment 6 hours at 60 DEG C.Adopt deionized water by the washing of high molecular polymer perforated membrane to neutral, the high molecular polymer perforated membrane of acquisition surface hydrophilic.
2) 7.9g potassium permanganate and 7.1g sodium sulphate are dispersed in 60mL deionized water, obtain chemical bath deposition reactant liquor.Be impregnated in above-mentioned chemical bath deposition reactant liquor by the high molecular polymer perforated membrane of surface hydrophilic again, the chemical bath deposition time is 0.5 hour.Then high molecular polymer perforated membrane is separated with solution, with deionized water cyclic washing for several times, being placed in temperature is that the baking oven of 60 DEG C is dried, obtains containing manganese precursor thin-film.
3) get that 1g is dried is placed in crucible containing manganese precursor thin-film, add 10mL containing 0.05g/mL water lithium chloride solution, then crucible is placed in the reacting furnace that temperature is 400 DEG C, pass into flow be the nitrogen of 400sccm as protective gas, react 4 hours.Finally obtain end product in 850 DEG C of calcinings after 6 hours in air atmosphere, be three-dimensional porous LiMn2O4 membrane electrode.Similar Fig. 1 of XRD collection of illustrative plates of this product.
With the method assembling simulated battery of obtained three-dimensional porous LiMn2O4 membrane electrode by embodiment 1, under 1C current density, its reversible capacity reaches 105mAh g
-1.
Embodiment 4
1) in the embodiment of the present invention, the preliminary treatment of high molecular polymer perforated membrane adopts following steps: take deionized water as solvent preparation 500mL strong oxidizing property acid solution, it is 1:1 mixing by the mol ratio of hydrochloric acid and sulfuric acid, then deionized water is added to 500mL, obtain 500mL strong oxidizing property acid solution, wherein the gross mass percentage of hydrochloric acid and sulfuric acid is 15%.High molecular polymer perforated membrane (polyethylene porous matter film, day east SUNMAP) is immersed in this strong oxidizing property acid solution, hydrophilicity-imparting treatment 6 hours at 60 DEG C.Adopt deionized water by the washing of high molecular polymer perforated membrane to neutral, the high molecular polymer perforated membrane of acquisition surface hydrophilic.
2) 3.2g potassium permanganate and 2.9g sodium sulphate are dispersed in 80mL deionized water, obtain chemical bath deposition reactant liquor.Be impregnated in above-mentioned chemical bath deposition reactant liquor by the high molecular polymer perforated membrane of surface hydrophilic again, the chemical bath deposition time is 45 minutes.Then high molecular polymer perforated membrane is separated with solution, with deionized water cyclic washing for several times, being placed in temperature is that the baking oven of 55 DEG C is dried, obtains containing manganese precursor thin-film.
3) get that 0.5g is dried is placed in crucible containing manganese precursor thin-film, add 5mL containing 0.1g/mL lithium carbonate ethanolic solution, then crucible is placed in the reacting furnace that temperature is 400 DEG C, pass into flow be the argon gas of 200sccm as protective gas, react 1 hour.Finally obtain end product in 750 DEG C of calcinings after 10 hours in air atmosphere, be three-dimensional porous LiMn2O4 membrane electrode.Similar Fig. 1 of XRD collection of illustrative plates of this product.
With the method assembling simulated battery of obtained three-dimensional porous LiMn2O4 membrane electrode by embodiment 1, under 0.5C current density, its reversible capacity reaches 124mAh g
-1.
Claims (10)
1. a preparation method for three-dimensional porous LiMn2O4 membrane electrode, is characterized in that, comprise the following steps:
1) be immersed in strong oxidizing property acid solution by high molecular polymer perforated membrane, hydrophilicity-imparting treatment 0.5-24 hour under 40-80 DEG C of condition, washing, to neutral, obtains the high molecular polymer perforated membrane of surface hydrophilic;
2) prepare the mixed solution that be made up of potassium permanganate, sodium sulphate and water as chemical plating fluid, adopt chemical bath deposition method, by the high molecular polymer porous film surface of manganese-oxide deposition at surface hydrophilic, obtain containing manganese precursor thin-film;
3) will be impregnated in lithium-containing solution containing manganese precursor thin-film, in 250-400 DEG C of reaction 0.5-8 hour under protective atmosphere, more in air atmosphere in 500-900 DEG C of reaction 1-10 hour, finally obtain three-dimensional porous LiMn2O4 membrane electrode.
2. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1, it is characterized in that, step 1) in, described high molecular polymer perforated membrane is polypropylene screen, polyethylene film or polypropylene, polyethylene composite wood plasma membrane, and thickness is less than 50 μm.
3. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1, is characterized in that, step 1) in, described strong oxidizing property acid solution is at least one in hydrochloric acid solution, salpeter solution, sulfuric acid solution.
4. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1, it is characterized in that, step 2) in, in described chemical plating fluid, the mol ratio of potassium permanganate and sodium sulphate is 1:0.8 ~ 1.2, and in described chemical plating fluid, the total concentration of potassium permanganate and sodium sulphate is 0.01-1mol/L.
5. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1, it is characterized in that, step 2) in, described chemical bath deposition method is specific as follows: the high molecular polymer perforated membrane of surface hydrophilic is immersed chemical plating fluid, soak after 0.5-1 hour, high molecular polymer perforated membrane is separated with solution, namely obtains containing manganese precursor thin-film after washing, drying.
6. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1, it is characterized in that, step 3) in, described lithium-containing solution is at least one in lithium hydroxide aqueous solution, water lithium chloride solution, the lithium acetate aqueous solution, the lithium nitrate aqueous solution, the lithium sulfate aqueous solution, lithium carbonate ethanolic solution.
7. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1, is characterized in that, step 3) in, the concentration of described lithium-containing solution is not more than 0.1g/mL.
8. the preparation method of three-dimensional porous LiMn2O4 membrane electrode according to claim 1; it is characterized in that; step 3) in; to be impregnated in lithium-containing solution containing manganese precursor thin-film; in 300 DEG C of reactions 2 hours under protective atmosphere; again in air atmosphere in 800 DEG C of reactions 8 hours, finally obtain three-dimensional porous LiMn2O4 membrane electrode.
9. three-dimensional porous LiMn2O4 membrane electrode prepared by the preparation method according to any one of claim 1 ~ 8.
10. three-dimensional porous LiMn2O4 membrane electrode according to claim 9 is in the application as lithium ion cell positive.
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