CN106299242A - A kind of porous spherical LiMn2o4preparation method - Google Patents
A kind of porous spherical LiMn2o4preparation method Download PDFInfo
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- CN106299242A CN106299242A CN201610673047.3A CN201610673047A CN106299242A CN 106299242 A CN106299242 A CN 106299242A CN 201610673047 A CN201610673047 A CN 201610673047A CN 106299242 A CN106299242 A CN 106299242A
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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
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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
- H01M4/139—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
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
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Abstract
A kind of porous spherical LiMn2O4Preparation method, the manganese acetate solution of 100mL 1mol/L is injected in beaker, beaker is placed in oil bath and is heated to 80 85 DEG C, subsequently mixed for the sodium carbonate/sodium hydroxide (mass ratio 1:3) of 50mL 2mol/L liquid is joined in beaker according to the 3 seconds speed of every, open stirring simultaneously；After starting to instill 10mL hydroperoxidation 2.5 2.75h after mixed drop adds, stop i.e. can get the mixed sediment of manganese carbonate and manganese dioxide；After being rinsed well by mixed sediment deionized water, 105 110 DEG C of drying obtain precursor；By the mol ratio of 1:2, precursor being carried out ball milling with lithium nitrate mix, high temperature sintering 8.5 9.5h in 650 700 DEG C of air atmospheres, after natural cooling, to obtain final product subsequently.The invention has the beneficial effects as follows: synthesis technique is simple, reaction condition is gentle, and production cost is relatively low, favorable repeatability, and material has the chemical property of excellence.
Description
Technical field
The present invention relates to material synthesis method, particularly a kind of porous spherical LiMn2O4Preparation method.
Background technology
The energy occupies highly important position in the development of modern society.The fossils such as traditional oil, coal and natural gas
Fuel the most gradually can not meet the development need of global economy society, and additionally traditional energy consumption is along with serious air pollution
And greenhouse effect.Under such overall background, the clean energy resource of exploitation a new generation causes global concern, such as water energy,
Wind energy, solar energy, tide energy and geothermal energy etc., but these energy also exist the unstability in time and space, how to this
It is the importance that new energy development utilizes that a little new forms of energy carry out reasonable distribution.The most rational solution is exactly will at present
Unnecessary energy first stores, and carries out rational Distribution utilization needs when again.Such as, electricity is first converted solar energy into
Can, the storability followed by electric energy carries out reasonable distribution utilization.Lithium ion battery is current maximally effective energy storage
Equipment, lithium ion battery has an open circuit, and charge/discharge capacity is big, voltage is high, self discharge is little, environmental friendliness and the plurality of advantages such as convenient,
And lithium ion battery is widely used in portable electric appts, nowadays hybrid vehicle, pure electric automobile are at large-scale electricity storage station
It is widely applied Deng have also been obtained on main equipment.Lithium ion battery mainly include positive electrode, negative material, electrolyte, every
Film, collector and shell, wherein positive electrode accounts for the 30% of the whole cost of raw material；In current lithium ion battery technology,
The running voltage of lithium ion battery, energy density and high rate performance are mainly by theoretical capacity and the macroscopic property institute of positive electrode
Determine, so the research and development of positive electrode are the emphasis of lithium ion battery development.
In the anode material for lithium-ion batteries used at present, spinelle LiMn2O4There is low cost, safety, raw material rich
Richness and advantages of environment protection so that it is become the most promising positive electrode.But spinelle LiMn2O4In cyclic process
Owing to the erosion of dissolving of Mn causes its capacity attenuation the most at high temperature capacity attenuation to compare with Jahn-Teller effect
Seriously.Currently mainly reduce the molten of Mn by doping, nanorize, the compound/method such as cladding and nucleocapsid of material with carbon element
Solve and corrode and suppression Jahn-Teller effect, and then improve its chemical property.
Summary of the invention
The technical problem to be solved is to provide a kind of porous spherical LiMn2O4Preparation method, it is provided that a kind of
New synthetic method.
The synthetic method that the present invention uses, comprises the steps:
The manganese acetate solution of 100mL 1mol/L is injected in beaker, beaker is placed in oil bath and is heated to 80-85 DEG C, subsequently
Mixed for the sodium carbonate/sodium hydroxide (mass ratio 1:3) of 50mL 2mol/L liquid is joined in beaker according to the 3 seconds speed of every, with
Shi Kaiqi stirs；After starting after mixed drop adds to instill 10mL hydroperoxidation 2.5-2.75h, stop i.e. can get carbon
Acid manganese and the mixed sediment of manganese dioxide；Mixed sediment deionized water is rinsed well rear 105-110 DEG C of drying obtain
Precursor；By the mol ratio of 1:2, precursor is carried out ball milling with lithium nitrate mix, high in 650-700 DEG C of air atmosphere subsequently
Temperature sintering 8.5-9.5h, after natural cooling, to obtain final product.
The invention has the beneficial effects as follows: synthesis technique is simple, reaction condition is gentle, and production cost is relatively low, favorable repeatability,
Material has the chemical property of excellence.
Detailed description of the invention
Further illustrating present disclosure below in conjunction with example, as known by the technical knowledge, the present invention also can pass through other
The scheme without departing from the technology of the present invention feature describe, the most all within the scope of the present invention or equivalent the scope of the invention in
Change and be all included in the invention.
Embodiment 1:
The manganese acetate solution of 100mL 1mol/L is injected in beaker, beaker is placed in oil bath and is heated to 80-85 DEG C, subsequently
Mixed for the sodium carbonate/sodium hydroxide (mass ratio 1:3) of 50mL 2mol/L liquid is joined in beaker according to the 3 seconds speed of every, with
Shi Kaiqi stirs；Stop i.e. can get after starting after mixed drop adds to instill 10mL hydroperoxidation 2.5h manganese carbonate and
The mixed sediment of manganese dioxide；Mixed sediment deionized water is rinsed well rear 105 DEG C of drying and obtains precursor；By front
Body carries out ball milling with lithium nitrate by the mol ratio of 1:2 and mixes, subsequently high temperature sintering 8.5h in 650 DEG C of air atmospheres, natural
After cooling, to obtain final product.
Embodiment 2:
The manganese acetate solution of 100mL 1mol/L is injected in beaker, beaker is placed in oil bath and is heated to 85 DEG C, subsequently will
The mixed liquid of the sodium carbonate/sodium hydroxide (mass ratio 1:3) of 50mL 2mol/L joins in beaker, simultaneously according to the 3 seconds speed of every
Open stirring；Stop i.e. can get after starting after mixed drop adds to instill 10mL hydroperoxidation 2.75h manganese carbonate and
The mixed sediment of manganese dioxide；Mixed sediment deionized water is rinsed well rear 110 DEG C of drying and obtains precursor；By front
Body carries out ball milling with lithium nitrate by the mol ratio of 1:2 and mixes, subsequently high temperature sintering 9.5h in 700 DEG C of air atmospheres, natural
After cooling, to obtain final product.
Exterior appearance uses field emission microscopy observation, is found out by observation, porous spherical LiMn2O4In spherical porous
Structure and morphology, and the size distribution of ball is uniform；Porous spherical LiMn simultaneously2O4It is by the nano-particle group of particle diameter about 200nm
Become, and this it appears that the surface of ball has the structure of porous.
Porous spherical LiMn by preparation2O4The contrast LiMn of active material and purchase2O4Active material powder, acetylene black
(conductive agent), polyvinylidene fluoride (PVDF binding agent) quality according to 84: 8: 8, than mix homogeneously, adds a certain amount of
N-methyl is criticized and is slightly burnt ketone (NMP), after the grinding uniform pulpous state of formation on tenaplate, is dried in the vacuum drying oven of 120 DEG C
12h, with correct amount after sheet-punching machine punching.
Experimental cell assembles in the glove box of full high-purity argon gas, moisture ＜ 2 × 10-6.With above-mentioned preparation
Electrode slice be positive pole, with Cel gard 2325 polypropylene microporous membrane as barrier film, metal lithium sheet is negative pole, 1mol/L
LiFP6/EC+EMC(volume ratio 1:1) it is electrolyte, dress up button cell (CR2032 type).Use battery test system to experiment
Room battery carries out constant current charge-discharge test, and charging/discharging voltage scope is 3.5-4.3V.By the record constant current charge-discharge time
Quality with electrode used therein active material, it can be deduced that the electrochemistry specific discharge capacity of sample.
By experiment, show that its first charge-discharge specific capacity is 120.88mAh/g(0.5C, 3.5～4.3V), efficiency
Up to more than 99%, after 100 circulations, capability retention is 92.1%；Porous spherical LiMn under the multiplying power of 5C2O4Put
Capacitance, up to 72mAh/g, absolutely proves the chemical property that prepared porous spherical LiMn2O4 is excellent.
Claims (1)
1. a porous spherical LiMn2O4Preparation method, comprise the steps: to note the manganese acetate solution of 100mL 1mol/L
Enter in beaker, beaker is placed in oil bath and is heated to 80-85 DEG C, subsequently by the sodium carbonate/sodium hydroxide of 50mL 2mol/L
(mass ratio 1:3) mixed liquid joins in beaker according to the 3 seconds speed of every, opens stirring simultaneously；Drop to be mixed is opened after adding
Stop i.e. can get the mixed sediment of manganese carbonate and manganese dioxide after beginning to instill 10mL hydroperoxidation 2.5-2.75h；Will
Mixed sediment deionized water is rinsed rear 105-110 DEG C of drying well and is obtained precursor；Precursor and lithium nitrate are pressed 1:2's
Mol ratio carries out ball milling mixing, subsequently high temperature sintering 8.5-9.5h in 650-700 DEG C of air atmosphere, after natural cooling, to obtain final product.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273564A (en) * | 1998-07-31 | 2000-11-15 | 三井金属矿业株式会社 | Process for producing spinel type lithium manganate |
| CN1289462A (en) * | 1998-11-30 | 2001-03-28 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary cell |
| EP1094034A1 (en) * | 1999-04-08 | 2001-04-25 | Mitsui Mining & Smelting Co., Ltd. | Method for preparing lithium manganate having spinel structure |
| CN104409719A (en) * | 2014-12-02 | 2015-03-11 | 兰州理工大学 | Porous spherical lithium manganate cathode material and preparation method thereof |
| CN105633500A (en) * | 2016-02-22 | 2016-06-01 | 四川天齐锂业股份有限公司 | Method for preparing ternary cathode material precursor by recycling lithium-ion battery material |
-
2016
- 2016-08-16 CN CN201610673047.3A patent/CN106299242A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273564A (en) * | 1998-07-31 | 2000-11-15 | 三井金属矿业株式会社 | Process for producing spinel type lithium manganate |
| CN1289462A (en) * | 1998-11-30 | 2001-03-28 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary cell |
| EP1094034A1 (en) * | 1999-04-08 | 2001-04-25 | Mitsui Mining & Smelting Co., Ltd. | Method for preparing lithium manganate having spinel structure |
| CN104409719A (en) * | 2014-12-02 | 2015-03-11 | 兰州理工大学 | Porous spherical lithium manganate cathode material and preparation method thereof |
| CN105633500A (en) * | 2016-02-22 | 2016-06-01 | 四川天齐锂业股份有限公司 | Method for preparing ternary cathode material precursor by recycling lithium-ion battery material |
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Application publication date: 20170104 |