CN105489879A - Preparation method for alkali metal ion modified manganese series oxide negative electrode material - Google Patents
Preparation method for alkali metal ion modified manganese series oxide negative electrode material Download PDFInfo
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- CN105489879A CN105489879A CN201511016059.0A CN201511016059A CN105489879A CN 105489879 A CN105489879 A CN 105489879A CN 201511016059 A CN201511016059 A CN 201511016059A CN 105489879 A CN105489879 A CN 105489879A
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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
- H01M4/36—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for an alkali metal ion modified manganese series oxide negative electrode material, and belongs to the technical field of a lithium ion battery negative electrode material. The preparation method for the alkali metal ion modified manganese series oxide negative electrode material comprises the following steps of 1) adding the manganese series metal oxide or a decomposable precursor of the manganese series oxide, and alkali metal salt into water, stirring at a temperature of 50-70 DEG C until the mixture is dry, and grinding the obtained product to obtain an intermediate product composite material; and 2) performing thermal insulation on the intermediate product composite material in an inert atmosphere at a temperature of 400-600 DEG C for 0.5-6h, and cooling to obtain the alkali metal ion modified manganese series oxide negative electrode material. The negative electrode material is excellent in electrochemical cycling performance and rate capability; the discharge capacity for the first time at the current density of 375mA/g can reach 1359mAh/g; the discharge capacity can be still greater than 1170mAh/g after the negative electrode material is subjected to 100 times of circulation; and in addition, the preparation method is simple in preparation process, simple and convenient to operate, low in cost and environment-friendly, and suitable for small-and-medium-sized electronic equipment for the lithium ion battery, a power battery and the like.
Description
Technical field
The present invention relates to the preparation method that a kind of alkali metal ion modifies manganese series oxides negative material, belong to technical field of lithium ion battery negative.
Background technology
Lithium ion battery has high power capacity, high-energy-density as new green power, has extended cycle life, the advantage such as self-discharge rate is low, security performance good, memory-less effect, has broad application prospects in portable electric appts, electric automobile, office automation, space technology, medicine equipment, national defense industry, household electrical appliance etc.
Electrode material determines lithium ion battery energy density, one of fail safe and the key factor in life-span, and the high performance of negative material to lithium ion battery of research and development high power capacity and long circulation life plays a part very important.Business-like negative material mainly graphite-like material with carbon element in the market, the advantages such as voltage is low, stable circulation that it has.But its theoretical specific capacity is only 372mAh/g, be difficult to meet the requirement to electrode material high power capacity.In addition, graphite-like material with carbon element easily produces Li dendrite in cyclic process, easily causes safety issue, so be not suitable for electrokinetic cell.In recent years, transition metal oxide is (as MnO, Mn
2o
3, Mn
3o
4, NiO, CoO, Co
3o
4, Fe
2o
3, Fe
3o
4deng) cause the extensive concern of people because of its higher theoretical specific capacity and good fail safe.But transition metal oxide is in lithiumation or go to there is larger volumetric expansion in lithiumation process, easily cause electrode material powdered, and the conductivity of transition metal oxide self is poor, in charge and discharge process, easily makes amount of activated material lose effective electrical contact, reduce its cycle performance.
Compare other transition metal oxide, the theoretical specific capacity of manganese series oxides is high, is about 2 times of graphite cathode material, and has lower de-lithium current potential.Having the advantages such as with low cost, abundant raw material, safety and environmental protection in addition, is the lithium cell cathode material having prospect.But the first coulombic efficiency of manganese series oxides in cyclic process is lower, change in volume is large, and cyclical stability is poor.At present, the method that modification manganese series oxides is conventional carries out nanometer process to material, reduces lithiumation or go the volumetric expansion in lithiumation process; Or the material with carbon element good with conductivity (as active carbon, carbon nano-tube, Graphene etc.) carries out compound, alleviates its change in volume; Or its conductivity of rare-earth metal doped enhancing.Such as can adopt synthesis MnO nano wire, MnO-carbon nano tube compound material, the MnO-graphene composite materials etc. such as sol-gal process, hydro thermal method, vapour deposition process, spray drying process, microemulsion method, but synthetic operation is complicated, material cost is high, length consuming time.
Summary of the invention
The object of this invention is to provide the preparation method that a kind of alkali metal ion modifies manganese series oxides negative material.
In order to realize above object, the technical solution adopted in the present invention is:
Alkali metal ion modifies the preparation method of manganese series oxides negative material, comprises the following steps:
1) get the easy decomposition presoma of manganese series metal oxide or manganese series metal oxide, be added to the water together with alkali metal salt, be stirred to dry at temperature 50 ~ 70 DEG C, after grinding, obtain intermediate product composite material;
2), in inert atmosphere, get intermediate product composite material and be incubated 0.5 ~ 6 hour at temperature 400 ~ 600 DEG C, cool and get final product.
Step 1) in manganese series metal oxide be one or more in manganese oxide, manganese sesquioxide managnic oxide, mangano-manganic oxide etc.
Step 1) in the easy decomposition presoma of manganese series metal oxide can adopt the easily decomposed substance such as carbonate, hydroxide, oxalates of manganese system metal, pattern can be submicron spherical, threadiness or Nanoparticulate, tool loose structure.Preferred spherical carbonate precursor, its processing characteristics is good, and tap density is high; Preferably easily scale be raw material with manganese system metal sulfate and sodium carbonate liquid phase deposition synthesize, react complete, isolate precipitation, washing, drying.Washing can adopt water and ethanol successively, and drying can adopt vacuumize, as at temperature 50 ~ 80 DEG C dry 6 ~ 12 hours.
Step 1) in alkali metal salt be lithium, sodium, potassium, the carbonate of rubidium, oxalates or acetate.
Step 2) in the amount ratio of easy decomposition presoma of alkali metal salt and manganese series metal oxide or manganese series metal oxide be m (alkali metal salt): m (manganese series metal oxide or easily decompose presoma)=1:15 ~ 50.The concentration preferably 0.4 ~ 1mol/L of alkali carbonate.
Step 2) in inert atmosphere can adopt nitrogen or argon gas, flow velocity is 0.5 ~ 3L/min.
Beneficial effect of the present invention:
In the present invention, alkali metal ion modifies electrochemistry cycle performance and the high rate performance that manganese series oxides negative material has excellence, under 375mA/g current density, discharge capacity reaches 1359mAh/g first, still more than 1170mAh/g is stabilized in after 100 circulations, be applicable to the little medium-sized electronic equipment such as lithium ion battery, electrokinetic cell, there is good prospect of industrial development.
In the present invention, to modify the preparation technology of manganese series oxides negative material simple for alkali metal ion, and easy and simple to handle, production cost is low, environmentally friendly, material structure and electrical property reproducible, be suitable for large-scale production and application.
Accompanying drawing explanation
Fig. 1 is the XRD figure that in embodiment 1, sodium ion modifies manganese oxide negative material;
Fig. 2 is the SEM figure that sodium ion modifies manganese oxide negative material;
Fig. 3 adopts sodium ion modification manganese oxide negative material in embodiment 1 to prepare the voltage capacity figure of lithium battery;
Fig. 4 is the cycle performance figure of lithium battery.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
Alkali metal ion modifies the preparation method of manganese series oxides negative material, comprises the following steps:
1) the easy decomposition presoma of manganese series metal oxide is prepared
4.225g (0.025mol) manganese sulfate and 2.319g (0.0218mol) sodium carbonate are dissolved in 70mL deionized water respectively, be stirred to dissolving, manganese sulfate solution is poured in sodium carbonate liquor fast, 600r/min is centrifugal, precipitation is successively with distilled water and ethanol washing, and vacuumize 10 hours under temperature 60 C, obtain persursor material;
2) take 0.3g persursor material and 0.006g sodium carbonate (by quality ratio, presoma: sodium carbonate=50:1), join in 20mL distilled water, be stirred to dry under temperature 50 C, grinding, obtains intermediate product composite material;
3) under flow 1L/min nitrogen protection, intermediate product composite material is placed in tube furnace, rises to 450 DEG C with the heating rate of 5 DEG C/min from room temperature, be incubated 3 hours, then naturally cool to room temperature with stove, obtain sodium ion and modify manganese oxide negative material.
Get above-mentioned sodium ion modification manganese oxide negative material and carry out characterization test, Figure 1 shows that the XRD figure of negative material, diffraction maximum from left to right 35.0 °, 40.6 °, 58.7 °, 70.2 ° and 73.8 ° (111), (200), (220), (311) and (222) feature crystal faces corresponding respectively to MnO.Figure 2 shows that the SEM figure of negative material, as can be seen from the figure, negative material is made up of porous spherical and bar-shaped two kinds of different-shapes.
Get above-mentioned sodium ion to modify manganese oxide negative material and prepare negative pole, be positive pole with lithium metal, Celgared2400 is barrier film, 1mol/LLiPF simultaneously
6solution is that lithium ion battery prepared by electrolyte, and carries out charge-discharge performance test, and its voltage capacity figure and cycle performance figure is shown in Fig. 3 and Fig. 4 respectively.Be not difficult to find out from figure, lithium battery first discharge specific capacity reaches 1359mAh/g, charge specific capacity 998mAh/g, and the specific discharge capacity after 150 times that circulates still remains on 1170mAh/g, and capability retention is 86.1%.
Embodiment 2
Alkali metal ion modifies the preparation method of manganese series oxides negative material, comprises the following steps:
1) the easy decomposition presoma of manganese series metal oxide is prepared
5.04g (0.04mol) manganese chloride and 3.71g (0.035mol) sodium carbonate are dissolved in 50mL deionized water respectively, be stirred to dissolving, manganese chloride solution is poured in sodium carbonate liquor fast, 700r/min is centrifugal, precipitation is successively with distilled water and ethanol washing, and vacuumize 10 hours under temperature 60 C, obtain persursor material;
2) take 0.68g persursor material and 0.024g lithium carbonate (by quality ratio, presoma: lithium carbonate=30:1), join in 30mL distilled water, be stirred to dry under temperature 60 C, grinding, obtains intermediate product composite material;
3) under flow 0.5L/min nitrogen protection, intermediate product composite material is placed in tube furnace, rises to 400 DEG C with the heating rate of 10 DEG C/min from room temperature, be incubated 4 hours, then naturally cool to room temperature with stove, obtain lithium ion and modify manganese oxide negative material.
Get above-mentioned lithium ion to modify manganese oxide negative material and prepare lithium ion battery, recording its first discharge specific capacity is 1235mAh/g, and the specific discharge capacity after 150 times that circulates is 862mAh/g.
Embodiment 3
Alkali metal ion modifies the preparation method of manganese series oxides negative material, comprises the following steps:
1) the easy decomposition presoma of manganese series metal oxide is prepared
3.46g (0.02mol) manganese acetate and 1.86g (0.0175mol) sodium carbonate are dissolved in 60mL deionized water respectively, be stirred to dissolving, manganese acetate solution is poured in sodium carbonate liquor fast, 750r/min is centrifugal, precipitation is successively with distilled water and ethanol washing, and vacuumize 12 hours under temperature 60 C, obtain persursor material;
2) take 0.5g persursor material and 0.036g potash (by quality ratio, presoma: potash=15:1), join in 25mL distilled water, be stirred to dry under temperature 70 C, grinding, obtains intermediate product composite material;
3) under flow 3L/min nitrogen protection, intermediate product composite material is placed in tube furnace, rises to 500 DEG C with the heating rate of 5 DEG C/min from room temperature, be incubated 5 hours, then naturally cool to room temperature with stove, obtain potassium ion and modify manganese oxide negative material.
Get above-mentioned potassium ion to modify manganese oxide negative material and prepare lithium ion battery, recording its first discharge specific capacity is 1023mAh/g, and the specific discharge capacity after 150 times that circulates is 795mAh/g.
Embodiment 4
Alkali metal ion modifies the preparation method of manganese series oxides negative material, comprises the following steps:
1) the easy decomposition presoma of manganese series metal oxide is prepared
4.225g (0.025mol) manganese sulfate and 2.319g (0.0218mol) sodium carbonate are dissolved in 70mL deionized water respectively, be stirred to dissolving, manganese sulfate solution is poured in sodium carbonate liquor fast, 600r/min is centrifugal, precipitation is successively with distilled water and ethanol washing, and vacuumize 12 hours under temperature 60 C, obtain persursor material;
2) under flow 3L/min nitrogen protection, persursor material is placed in tube furnace, rises to 450 DEG C with the heating rate of 5 DEG C/min from room temperature, be incubated 5 hours, then naturally cool to room temperature with stove, obtain manganese oxide presoma;
3) take 0.2g manganese oxide presoma and 0.006g sodium carbonate (by quality ratio, presoma: sodium carbonate=33.3:1), join in 20mL distilled water, be stirred to dry under temperature 50 C, grinding, obtains intermediate product composite material;
4) under flow 2L/min nitrogen protection, intermediate product composite material is placed in tube furnace, rises to 600 DEG C with the heating rate of 5 DEG C/min from room temperature, be incubated 3 hours, then naturally cool to room temperature with stove, obtain sodium ion and modify manganese oxide negative material.
Get above-mentioned sodium ion to modify manganese oxide negative material and prepare lithium ion battery, recording its first discharge specific capacity is 1197mAh/g, and the specific discharge capacity after 150 times that circulates is 835mAh/g.
Embodiment 5
Alkali metal ion modifies the preparation method of manganese series oxides negative material, comprises the following steps:
1) the easy decomposition presoma of manganese series metal oxide is prepared
3.46g (0.02mol) manganese acetate and 1.86g (0.0175mol) sodium carbonate are dissolved in 60mL deionized water respectively, be stirred to dissolving, manganese acetate solution is poured in sodium carbonate liquor fast, 750r/min is centrifugal, precipitation is successively with distilled water and ethanol washing, and vacuumize 10 hours under temperature 60 C, obtain persursor material;
2) under flow 3L/min nitrogen protection, persursor material is placed in tube furnace, rises to 450 DEG C with the heating rate of 5 DEG C/min from room temperature, be incubated 5 hours, then naturally cool to room temperature with stove, obtain manganese oxide presoma;
3) take 0.2g manganese oxide presoma and 0.005g sodium carbonate (by quality ratio, presoma: sodium carbonate=25:1), join in 25mL distilled water, be stirred to dry under temperature 70 C, grinding, obtains intermediate product composite material;
4) under flow 3L/min nitrogen protection, intermediate product composite material is placed in tube furnace, rises to 500 DEG C with the heating rate of 5 DEG C/min from room temperature, be incubated 5 hours, then naturally cool to room temperature with stove, obtain sodium ion and modify manganese oxide negative material.
Get above-mentioned sodium ion to modify manganese oxide negative material and prepare lithium ion battery, recording its first discharge specific capacity is 1679mAh/g, and the specific discharge capacity after 150 times that circulates is 949mAh/g.
Claims (7)
1. alkali metal ion modifies the preparation method of manganese series oxides negative material, it is characterized in that: comprise the following steps:
1) get the easy decomposition presoma of manganese series metal oxide or manganese series metal oxide, be added to the water together with alkali metal salt, be stirred to dry at temperature 50 ~ 70 DEG C, after grinding, obtain intermediate product composite material;
2), in inert atmosphere, get intermediate product composite material and be incubated 0.5 ~ 6 hour at temperature 400 ~ 600 DEG C, cool and get final product.
2. preparation method according to claim 1, is characterized in that: step 1) in manganese series metal oxide be one or more in manganese oxide, manganese sesquioxide managnic oxide, mangano-manganic oxide.
3. preparation method according to claim 1, is characterized in that: step 1) in the easy decomposition presoma of manganese series metal oxide be the carbonate of manganese system metal, hydroxide or oxalates.
4. preparation method according to claim 1, is characterized in that: step 1) in alkali metal salt be lithium, sodium, potassium, the carbonate of rubidium, oxalates or acetate.
5. preparation method according to claim 1, is characterized in that: step 2) in the mass ratio of easy decomposition presoma of alkali metal salt and manganese series metal oxide or manganese series metal oxide be 1:15 ~ 50.
6. the preparation method according to claim 4 or 5, is characterized in that: step 1) in the concentration of alkali metal salt be 0.4 ~ 1mol/L.
7. preparation method according to claim 1, is characterized in that: step 2) in inert atmosphere be nitrogen or argon gas, flow velocity 0.5 ~ 3L/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111354942A (en) * | 2019-11-26 | 2020-06-30 | 焦作伴侣纳米材料工程有限公司 | Micron-sized rod-shaped lithium manganate and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305644A (en) * | 1998-05-11 | 2001-07-25 | 杜拉塞尔公司 | Lithiated manganese oxide |
| US6982048B1 (en) * | 2001-09-11 | 2006-01-03 | The United States Of America As Represented By The Secretary Of The Army | Potassium stabilized manganese dioxide for lithium rechargeable batteries |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305644A (en) * | 1998-05-11 | 2001-07-25 | 杜拉塞尔公司 | Lithiated manganese oxide |
| US6982048B1 (en) * | 2001-09-11 | 2006-01-03 | The United States Of America As Represented By The Secretary Of The Army | Potassium stabilized manganese dioxide for lithium rechargeable batteries |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111354942A (en) * | 2019-11-26 | 2020-06-30 | 焦作伴侣纳米材料工程有限公司 | Micron-sized rod-shaped lithium manganate and preparation method and application thereof |
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