CN104009239A - Nano carbon doped manganese-based solid solution anode material and preparation method thereof - Google Patents
Nano carbon doped manganese-based solid solution anode material and preparation method thereof Download PDFInfo
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- CN104009239A CN104009239A CN201310679959.8A CN201310679959A CN104009239A CN 104009239 A CN104009239 A CN 104009239A CN 201310679959 A CN201310679959 A CN 201310679959A CN 104009239 A CN104009239 A CN 104009239A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
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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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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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 relates to a nano carbon doped manganese-based solid solution anode material and a preparation method thereof. The preparation method is achieved by nano carbon doping, and comprises the particular steps of mixing lithium salt, manganese salt, nickel salt, cobalt salt and nano carbon at a certain stoichiometric ratio by a combustion method, heating the mixed matter at a certain temperature until the mixed matter becomes transparent viscous slurry, roasting the transparent viscous slurry in a stainless steel boat until the transparent viscous slurry is converted into foamed ash, sintering the ash for some time in a high-temperature air atmosphere after the ash is pulverized, and then obtaining the nano carbon doped solid solution material. According to the material and the preparation method, a solid solution is doped with graphene or a carbon nano tube, so that the conductivity and the rate capability of the material can be improved on one hand, and the electrochemical cyclic stability of the material can be improved on the other hand.
Description
Technical field
The present invention relates to new energy materials technical field, be specifically related to manganese based solid solution positive electrode of a kind of nano-sized carbon doping and preparation method thereof.
Background technology
Lithium ion battery has advantages of that voltage is high, specific energy large, has extended cycle life, and is widely used in portable electronics.And the LiCoO that commercialization is at present used
2because the few price of reserves is high, the more massive application of lithium ion battery is restricted.Li (Co – Ni – Mn) O
2sill has height ratio capacity (200 ~ 300 mAh/g) and receives increasing concern compared with low price, is positive electrode current commercialization main product LiCoO
2well substitute.In addition, LCMNO material has higher structural stability, in embedding lithium-Tuo lithium process repeatedly, can keep good layer structure; LCMNO material also shows good thermal stability, even under 90 ° of C, places 1 week, and character also can not decay.
Recently, there is researcher to be coated Co by surface
3(PO
4)
2improve capacity and the cyclical stability of LCMNO.In addition nano level LCMNO is also used for filling out and covers micron order LiCoO
2space, to improving its capacity and high rate performance.
Material with carbon element gradually be used in positive electrode conductivity and the high rate performance to improve positive electrode.Wherein carbon nano-tube and Graphene are considered to the most promising nano material of 21 century.Graphene be a kind of by carbon atom with sp
2the New Two Dimensional atomic crystal that the monoatomic layer that hydridization connects forms, has the physicochemical properties of many uniquenesses, as specific area reaches 2630 m
2/ g, fracture strength reach 200000 cm up to/125 GPa, carrier mobility
2/ Vs, thermal conductivity reach 5000 W/mk etc.As the interpolation phase time of composite material, not only can improve the mechanical property of composite material, can also give some special performances such as composite material is antistatic, conduction, suction ripple simultaneously.Carbon nano-tube is that one has special construction (radial dimension is nanometer scale, axial dimension can reach micron dimension) One-dimensional Quantum material, there is typical stratiform hollow structure feature, carbon nano-tube can regard that graphene sheet layer is curling as and form, and the same with Graphene have high-modulus, high strength, high conductivity and a high heat conductance.LCMNO is adulterated by Graphene or carbon nano-tube, the conductivity that is conducive on the one hand to improve LCMNO improves its high rate performance, and the structural framework that can stablize on the other hand LCMNO improves its electrochemistry cyclical stability.
Summary of the invention
Object of the present invention is just being to provide that a kind of reaction time is short, and technique is simple, manganese based solid solution positive electrode of nano-sized carbon doping that can suitability for industrialized production and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of the manganese based solid solution positive electrode of described a kind of nano-sized carbon doping is by the mixing salt solution of certain stoichiometric proportion configuration lithium salts, manganese salt, nickel salt, cobalt salt; The nano-sized carbon of certain mass percent is joined in above-mentioned mixing salt solution 1, produce mixture 1; Mixture 1 is heated at a certain temperature until become transparent stickiness mud; Stickiness mud is placed in to stainless steel boat roasting until be converted into foamed ashes; After upper gained ashes are clayed into power, under high temperature air atmosphere, sintering certain hour obtains the solid-solution material that nano-sized carbon is adulterated.
Above-mentioned metal salt solution is the mixed solution of nitrate and acetate.
The total concentration of the metal ion solution in above-mentioned mixing salt solution 1 is 1 – 5 mol/L.
The percentage of above-mentioned nano-sized carbon is 2% – 10%, and nano-sized carbon comprises Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and Graphene.
The heating-up temperature of above-mentioned mixture 1 is 200 ° of C of 100 –.
Above-mentioned sintering temperature is 500 ° of C of 400 –.
Above-mentioned sintering temperature is controlled at 1000 ° of C of 800 –, roasting time 2-6h, and heating rate is 3-10 ° of C/min.
Advantage of the present invention: the present invention adopts combustion method to prepare solid solution cathode material, and the reaction time is short, and technique is simple, can suitability for industrialized production.Adulterate by Graphene or carbon nano-tube, the conductivity that is conducive on the one hand to improve solid-solution material improves its high rate performance, and the structural framework that can stablize on the other hand solid-solution material improves its electrochemistry cyclical stability.
Brief description of the drawings
Fig. 1 is the solid solution Li of Graphene doping of the present invention
1.2(Mn
0.5ni
0.2co
0.1) O
2low power and high power SEM figure;
Fig. 2 is solid solution Li of the present invention
1.2(Mn
0.5ni
0.2co
0.1) O
2multiplying power recycle ratio before doping and after doping.
Embodiment
Embodiment 1 (comparative example)
Solid solution Li
1.2(Mn
0.5ni
0.2co
0.1) O
2preparation process
(1) by the LiCH of proportional arrangement 2 mol/L of stoichiometric proportion 0.9:0.3:0.5:0.2:0.1
3cO
2, LiNO
3, Mn (CH
3cO
2)
2, Ni (NO
3)
2, Co (NO
3)
2salting liquid.
(2) said mixture is heated until become transparent stickiness mud under 150 ° of C.
(3) stickiness mud is placed in to 400 ° of C roastings of stainless steel boat until be converted into foamed ashes.
(4) above-mentioned substance is pulverized last under 850 ° of C air atmospheres sintering 3h obtain the Li of Graphene doping
1.2(Mn
0.5ni
0.2co
0.1) O
2material.
Embodiment 2
The solid solution Li of Graphene doping
1.2(Mn
0.5ni
0.2co
0.1) O
2preparation process
(1) by the LiCH of proportional arrangement 2 mol/L of stoichiometric proportion 0.9:0.3:0.5:0.2:0.1
3cO
2, LiNO
3, Mn (CH
3cO
2)
2, Ni (NO
3)
2, Co (NO
3)
2salting liquid.
(2) Graphene that is 5% by mass percent joins in above-mentioned mixing salt solution, stirs.
(3) said mixture is heated until become transparent stickiness mud under 150 ° of C.
(4) stickiness mud is placed in to 400 ° of C roastings of stainless steel boat until be converted into foamed ashes.
(5) above-mentioned substance is pulverized last under 850 ° of C air atmospheres sintering 3h obtain the Li of Graphene doping
1.2(Mn
0.5ni
0.2co
0.1) O
2material.
Embodiment 3
The solid solution Li of Single Walled Carbon Nanotube doping
1.2(Mn
0.5ni
0.2co
0.1) O
2preparation process
(1) by the LiCH of proportional arrangement 2 mol/L of stoichiometric proportion 0.9:0.3:0.5:0.2:0.1
3cO
2, LiNO
3, Mn (CH
3cO
2)
2, Ni (NO
3)
2, Co (NO
3)
2salting liquid.
(2) Single Walled Carbon Nanotube that is 4% by mass percent joins in above-mentioned mixing salt solution, stirs.
(3) said mixture is heated until become transparent stickiness mud under 150 ° of C.
(4) stickiness mud is placed in to 400 ° of C roastings of stainless steel boat until be converted into foamed ashes.
(5) above-mentioned substance is pulverized last under 850 ° of C air atmospheres sintering 3h obtain the Li of Single Walled Carbon Nanotube doping
1.2(Mn
0.5ni
0.2co
0.1) O
2material.
Embodiment 4
The solid solution Li of multi-walled carbon nano-tubes doping
1.2(Mn
0.4ni
0.25co
0.15) O
2preparation process
(1) by the LiCH of proportional arrangement 2 mol/L of stoichiometric proportion 0.9:0.3:0.4:0.25:0.15
3cO
2, LiNO
3, Mn (CH
3cO
2)
2, Ni (NO
3)
2, Co (NO
3)
2salting liquid.
(2) multi-walled carbon nano-tubes that is 7% by mass percent joins in above-mentioned mixing salt solution, stirs.
(3) said mixture is heated until become transparent stickiness mud under 150 ° of C.
(4) stickiness mud is placed in to 400 ° of C roastings of stainless steel boat until be converted into foamed ashes.
(5) above-mentioned substance is pulverized last under 800 ° of C air atmospheres sintering 3h obtain the Li of multi-walled carbon nano-tubes doping
1.2(Mn
0.5ni
0.2co
0.1) O
2material.
Fig. 1 is the solid solution Li of Graphene doping of the present invention
1.2(Mn
0.5ni
0.2co
0.1) O
2low power and high power SEM figure.By macrograph, we can observe this material monolithic and are graphene sheet layer structure, can see graphene film and be covered with equably one deck solid solution pellet from high power photo, and the size of particle is within the scope of 70nm – 180nm.
Fig. 2 is solid solution Li of the present invention
1.2(Mn
0.5ni
0.2co
0.1) O
2multiplying power recycle ratio before doping and after doping.By in figure, we can find out, the doping of Graphene can obviously improve Li
1.2(Mn
0.5ni
0.2co
0.1) O
2high rate capability, and multiplying power is higher, the effect of improvement is more obvious.
The present invention adopts combustion method to prepare solid solution cathode material, and the reaction time is short, and technique is simple, can suitability for industrialized production.Adulterate by Graphene or carbon nano-tube, the conductivity that is conducive on the one hand to improve solid-solution material improves its high rate performance, and the structural framework that can stablize on the other hand solid-solution material improves its electrochemistry cyclical stability.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned giving an example; those skilled in the art; in essential scope of the present invention, variation, remodeling, interpolation or the replacement made, all should belong to protection scope of the present invention.
Claims (7)
1. a preparation method for the manganese based solid solution positive electrode of nano-sized carbon doping, is characterized in that: the preparation method of the manganese based solid solution positive electrode of described a kind of nano-sized carbon doping is by the mixing salt solution of certain stoichiometric proportion configuration lithium salts, manganese salt, nickel salt, cobalt salt; The nano-sized carbon of certain mass percent is joined in above-mentioned mixing salt solution 1, produce mixture 1; Mixture 1 is heated at a certain temperature until become transparent stickiness mud; Stickiness mud is placed in to stainless steel boat roasting until be converted into foamed ashes; After upper gained ashes are clayed into power, under high temperature air atmosphere, sintering certain hour obtains the solid-solution material that nano-sized carbon is adulterated.
2. the preparation method of the manganese based solid solution positive electrode of a kind of nano-sized carbon doping according to claim 1, is characterized in that: described metal salt solution is the mixed solution of nitrate and acetate.
3. the preparation method of the manganese based solid solution positive electrode of a kind of nano-sized carbon doping according to claim 1, is characterized in that: the total concentration of the metal ion solution in described mixing salt solution 1 is 1 – 5 mol/L.
4. the preparation method of the manganese based solid solution positive electrode of a kind of nano-sized carbon doping according to claim 1, is characterized in that: the percentage of described nano-sized carbon is 2% – 10%, and nano-sized carbon comprises Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and Graphene.
5. the preparation method of the manganese based solid solution positive electrode of a kind of nano-sized carbon doping according to claim 1, is characterized in that: the heating-up temperature of described mixture 1 is 200 ° of C of 100 –.
6. the preparation method of the manganese based solid solution positive electrode of a kind of nano-sized carbon doping according to claim 1, is characterized in that: described sintering temperature is 500 ° of C of 400 –.
7. the preparation method of the manganese based solid solution positive electrode of a kind of nano-sized carbon doping according to claim 1, is characterized in that: described sintering temperature is controlled at 1000 ° of C of 800 –, roasting time 2-6h, and heating rate is 3-10 ° of C/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017005078A1 (en) * | 2015-07-09 | 2017-01-12 | 山东玉皇新能源科技有限公司 | Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof |
| CN106340642A (en) * | 2016-11-30 | 2017-01-18 | 烟台卓能电池材料股份有限公司 | Long-circulation and high-capacity lithium battery positive electrode material and preparing method |
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-
2013
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| US20050175529A1 (en) * | 1996-10-11 | 2005-08-11 | Massachusetts Institute Of Technology | Polymer electrolyte, intercalation compounds and electrodes for batteries |
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| WO2017005078A1 (en) * | 2015-07-09 | 2017-01-12 | 山东玉皇新能源科技有限公司 | Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof |
| CN106340642A (en) * | 2016-11-30 | 2017-01-18 | 烟台卓能电池材料股份有限公司 | Long-circulation and high-capacity lithium battery positive electrode material and preparing method |
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Application publication date: 20140827 |
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