CN1128480C - Preparation method of positive electrode material of lithium ion cell - Google Patents
Preparation method of positive electrode material of lithium ion cell Download PDFInfo
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- CN1128480C CN1128480C CN00117352A CN00117352A CN1128480C CN 1128480 C CN1128480 C CN 1128480C CN 00117352 A CN00117352 A CN 00117352A CN 00117352 A CN00117352 A CN 00117352A CN 1128480 C CN1128480 C CN 1128480C
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- temperature
- lithium
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- manganese
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- 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
- H01M4/485—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
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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 present invention relates to a preparation method of positive electrode materials of a lithium ion battery, which comprises: (1) manganese oxide or manganese salt is pretreated at temperature of 250 DEG C to 550 DEG C; (2) lithium salt of lithium carbonate, lithium nitrate, lithium hydroxide, etc. is mixed with manganese oxide of electrolytic manganese dioxide, chemical manganese dioxide, etc. and manganese salt; (3) the mixture is put in a crucible made of alumina ceramic to be treated at high temperature, and a pre-lithiation product is obtained; (4) after the pre-lithiation product is treated at high temperature and sieved, a product of LiMn2O4 is obtained. LiMn2O4 with excellent electrochemical performance, perfect crystal structure and low cost can be synthesized by the preparation method of the present invention.
Description
Technical field
The present invention relates to secondary cell, in more detail polymer Li-ion battery and lithium ion secondary battery anode material LiMn
2O
4The preparation method.
Background technology
Have high performance polymer lithium ion battery and lithium rechargeable battery and be widely used in the electronic apparatuss such as mobile communication, hand-held computer, portable instrument, also may be with power supply as electric automobile.But compare with other secondary cell, the price of lithium ion battery is too high to be the principal element of its development of restriction.In order to reduce the cost of lithium ion battery, the positive electrode of seeking a kind of low price, function admirable is one of main measure.Now the most noticeable is to having the LiMn of spinel structure
2O
4Research, hope finds a kind of technology preparation method simple, with low cost to synthesize LiMn
2O
4, obtain the high positive electrode of the ratio of performance to price and replace present being extensive use of but expensive LiCoO
2, in order to reduce the cost of lithium ion battery.
Duracell Co., Ltd has proposed the method that a kind of manufacturing has the lithium manganese oxide of spinel structure in Chinese patent application 97194637.This method comprises by making the reaction of manganese oxide and lithium hydroxide or lithium salts make the step of its pre-lithiumation, makes then the manganese oxide of pre-lithiumation react the formation lithium manganese oxide spinel in second step under higher temperature.This method will form pre-lithiumation thing by long liquid phase reactor earlier, and the technical process that adopts is too complicated, and the cycle of preparation is long, and production cost is increased.
The people such as J.M.Tarascom have reported with Li in [J.Electrochem.Soc.Vol.141 No.6, June 1994,1421-1431]
2CO
3Or LiNO
3With electrolytic manganese dioxide be the synthetic LiMn of raw material
2O
4This method is to descend to distinguish Synthetic 2s 4 hours and 48 hours twice at 800 ℃, cools off with the speed of 5-10 ℃/min then.The needed overlong time of this technology, thus also make the production cycle long, and production cost increases.
Summary of the invention
The objective of the invention is to provides a kind of lithium ion secondary battery anode material LiMn for the shortcoming that prior art exists
2O
4The preparation method, synthesize the product that chemical property is good, crystal structure is perfect, with low cost.
The preparation method of anode material for lithium-ion batteries of the present invention comprises the following steps:
(1) electrolytic manganese dioxide or chemical manganese bioxide carry out preliminary treatment 2-8 hour under 250-550 ℃ temperature, and be stand-by;
(2) lithium carbonate and pretreated electrolytic manganese dioxide or chemical manganese bioxide lithium in molar ratio: manganese=batching after carry out Ball milling mix 20-180 minute at 0.45: 0.55;
(3) be placed on after the mixture compacted in the aluminium oxide ceramics crucible, place blast furnace to be warmed up to the melt temperature of lithium carbonate with the programming rate of 1-10 ℃/min, constant temperature 0.5-16 hour, disperseed 10-30 minute with the slow cool to room temperature taking-up carrying out of furnace temperature secondary ball milling, obtain the product of pre-lithiumation;
(4) the product compacting with pre-lithiumation is placed in the alumina crucible, is warming up to 500-900 ℃ with the programming rate of 1-10 ℃/min, after constant temperature 0.5-48 hour, drops to the room temperature sampling with the rate of temperature fall of 1-10 ℃/min, namely obtains product LiMn after crossing 300 mesh sieves
2O
4
In the preparation method of anode material for lithium-ion batteries of the present invention, carry out Ball milling after allowing the lithium salts fusion and decomposition be impregnated in the lattice of manganese dioxide earlier, lithium salts is more even with the mixing of manganese salt, makes the high temperature solid state reaction of follow-up phase to carry out for a full due.Compare with other solid phase reaction method is resulting, the crystal formation of synthetic product is more perfect, has improved the chemical property of material to a certain extent.Particularly, its advantage is as follows:
1, method of the present invention can guarantee to have the advantages that production technology is simple, cost is low, be suitable for large-scale industrial production on constant product quality, the reliable basis.
2, the LiMn that makes
2O
4Have perfect spinel structure, no dephasign exists in the crystal structure of product.
3, the LiMn that makes
2O
4The chemical property of product is good.The material that makes with this method is that positive pole is made Experimental cell, with 0.5mA/cm
2Current density carry out charge-discharge test, first discharge specific capacity reaches 138mAh/g, the capability retention that circulates after 100 times also has more than 96% of initial reversible specific capacity.
4, material therefor is with low cost.As with electrolytic manganese dioxide and Li
2CO
3Be raw material, make 1 kilogram of LiMn
2O
4Only need 21.8 yuan/Kg of cost of material expense (by the price in July, 2000).
5, nontoxic, non-environmental-pollution.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Take by weighing Li
2CO
356.61g with through 4 hours electrolytic manganese dioxide of 400 ℃ of constant temperature preliminary treatment (EMD) 258g, Ball milling was mixed 100 minutes in ball mill, mixed material compacting is placed on alumina crucible, put into high temperature furnace, be elevated to 650 ℃ of constant temperature with the heating rate of 8 ℃/min from room temperature and take out with the slow cool to room temperature of furnace temperature after 12 hours and carry out subsequent segment and handle.Ball milling disperses to place alumina crucible after 20 minutes again, is elevated to 850 ℃ of constant temperature with the heating rate of 8 ℃/min from room temperature and is about to sample with the rate of temperature fall cool to room temperature of 2 ℃/min after 24 hours and took out 300 mesh sieves, namely obtains product LiMn
2O
4
Take prepared material as anodal, lithium metal is for to make Experimental cell to electrode, with 0.5mA/cm
2Charging and discharging currents density test.The first discharge reversible specific capacity of this material is 138mAh/g, and front 5 average specific discharge capacities that circulate are 136.8mAh/g.Making behind the battery with the capability retention after the 1C multiplying power 100%DOD charge and discharge cycles 100 times is 97.4% of initial reversible specific capacity.
Embodiment 2
Accurately take by weighing Li
2CO
356.61g with through 2 hours chemical manganese bioxide of 250 ℃ of constant temperature preliminary treatment (CMD) 258g, Ball milling was mixed 20 minutes in ball mill, mixed material compacting is placed on alumina crucible, put into high temperature furnace, be elevated to 700 ℃ of constant temperature with the heating rate of 10 ℃/min from room temperature and take out with the slow cool to room temperature of furnace temperature after 12 hours and carry out subsequent segment and handle.Ball milling disperses to place alumina crucible after 30 minutes again, is elevated to 500 ℃ of constant temperature with the heating rate of 8 ℃/min from room temperature and is about to sample with the rate of temperature fall cool to room temperature of 1 ℃/min after 48 hours and took out 300 mesh sieves, namely obtains product LiMn
2O
4
Take prepared material as anodal, lithium metal is for to make Experimental cell to electrode, with 0.5mA/cm
2Charging and discharging currents density test.The first discharge reversible specific capacity of this material is 98mAh/g, and front 5 average specific discharge capacities that circulate are 92mAh/g.
Embodiment 3
Take by weighing Li
2CO
356.61g with through 8 hours electrolytic manganese dioxide of 550 ℃ of constant temperature preliminary treatment (EMD) 258g, Ball milling was mixed 180 minutes in ball mill, mixed material compacting is placed on alumina crucible, put into high temperature furnace, be elevated to 650 ℃ of constant temperature with the heating rate of 1 ℃/min from room temperature and take out with the slow cool to room temperature of furnace temperature after 0.5 hour and carry out subsequent segment and handle.Ball milling disperses to place alumina crucible after 10 minutes again, is elevated to 900 ℃ of constant temperature with the heating rate of 1 ℃/min from room temperature and is about to sample with the rate of temperature fall cool to room temperature of 10 ℃/min after 0.5 hour and took out 300 mesh sieves, namely obtains product LiMn
2O
4
Take prepared material as anodal, lithium metal is for to make Experimental cell to electrode, with 0.5mA/cm
2Charging and discharging currents density test.The first discharge reversible specific capacity of this material is 84mAh/g, and front 5 average specific discharge capacities that circulate are 78mAh/g.
Embodiment 4
Accurately take by weighing Li
2CO
361.05g with through 4 hours electrolytic manganese dioxide of 400 ℃ of constant temperature preliminary treatment (EMD) 258g, Ball milling was mixed 120 minutes in ball mill, mixed material compacting is placed on alumina crucible, put into high temperature furnace, be elevated to 650 ℃ of constant temperature with the heating rate of 5 ℃/min from room temperature and take out with the slow cool to room temperature of furnace temperature after 12 hours and carry out subsequent segment and handle.Ball milling disperses to place alumina crucible after 30 minutes again, is elevated to 800 ℃ of constant temperature with the heating rate of 5 ℃/min from room temperature and is about to sample with the rate of temperature fall cool to room temperature of 2 ℃/min after 24 hours and took out 300 mesh sieves, namely obtains LiMn
2O
4
Take resulting material as anodal, metal lithium sheet is for to make Experimental cell to electrode, with 0.5mA/cm
2Charging and discharging currents density test.The first discharge reversible specific capacity of this material is 118.2mAh/g, and front 5 average specific discharge capacities that circulate are 115mAh/g.Making behind the battery with the capability retention after the 1C multiplying power 100%DOD charge and discharge cycles 100 times is 96.6% of initial reversible specific capacity.
Embodiment 5
Accurately take by weighing Li
2CO
354.39g with through 4 hours electrolytic manganese dioxide of 400 ℃ of constant temperature preliminary treatment (EMD) 258g, Ball milling was mixed 120 minutes in ball mill, mixed material compacting is placed on alumina crucible, put into high temperature furnace, be elevated to 650 ℃ of constant temperature with the heating rate of 5 ℃/min from room temperature and take out with the slow cool to room temperature of furnace temperature after 12 hours and carry out subsequent segment and handle.Ball milling disperses to place alumina crucible after 30 minutes again, is elevated to 850 ℃ of constant temperature with the heating rate of 5 ℃/min from room temperature and is about to sample with the rate of temperature fall cool to room temperature of 2 ℃/min after 24 hours and took out 300 mesh sieves, namely obtains LiMn
2O
4
With resulting material is positive pole, and metal lithium sheet is for to make Experimental cell to electrode, with 0.5mA/cm
2The density that discharges and recharges test.The first discharge reversible specific capacity of this material is 112mAh/g, and front 5 average specific discharge capacities that circulate are 106mAH/g.
Claims (1)
1, a kind of preparation method of anode material for lithium-ion batteries is characterized in that comprising the following steps:
(1) electrolytic manganese dioxide or chemical manganese bioxide carry out preliminary treatment 2-8 hour under 250-550 ℃ temperature, and be stand-by;
(2) lithium carbonate and pretreated electrolytic manganese dioxide or chemical manganese bioxide lithium in molar ratio: manganese=batching after carry out Ball milling mix 20-180 minute at 0.45: 0.55;
(3) be placed on after the mixture compacted in the aluminium oxide ceramics crucible, place blast furnace to be warmed up to the melt temperature of lithium carbonate with the programming rate of 1-10 ℃/min, constant temperature 0.5-16 hour, disperseed 10-30 minute with the slow cool to room temperature taking-up carrying out of furnace temperature secondary ball milling, obtain the product of pre-lithiumation;
(4) the product compacting with pre-lithiumation is placed in the alumina crucible, is warming up to 500-900 ℃ with the programming rate of 1-10 ℃/min, after constant temperature 0.5-48 hour, drops to the room temperature sampling with the rate of temperature fall of 1-10 ℃/min, namely obtains product LiMn after crossing 300 mesh sieves
2O
4
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CN00117352A CN1128480C (en) | 2000-08-14 | 2000-08-14 | Preparation method of positive electrode material of lithium ion cell |
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4172622B2 (en) * | 2002-04-11 | 2008-10-29 | 日鉱金属株式会社 | Lithium-containing composite oxide and method for producing the same |
CN102205989A (en) * | 2011-03-25 | 2011-10-05 | 江苏国泰锂宝新材料有限公司 | Preparation method for cathode material LiMn2O4 of cell |
CN102738455A (en) * | 2011-04-15 | 2012-10-17 | 深圳市比克电池有限公司 | Layered lithium manganate and preparation method thereof |
CN102856543B (en) * | 2012-09-14 | 2014-07-02 | 深圳先进技术研究院 | Lithium manganate material and preparation method thereof |
CN103187566B (en) * | 2013-03-28 | 2015-03-25 | 浙江大学 | Tubular lithium-rich anode material, preparation method and application thereof |
CN106784791A (en) * | 2016-12-30 | 2017-05-31 | 湘潭大学 | The preparation method of power type nanometer lithium manganate |
CN107482212A (en) * | 2017-07-03 | 2017-12-15 | 新乡市中天新能源科技股份有限公司 | A kind of preparation method of superelevation gram specific capacity spherical lithium manganate |
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