CN104993124A - Preparation method of laminated lithium nickel manganese oxide - Google Patents
Preparation method of laminated lithium nickel manganese oxide Download PDFInfo
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- CN104993124A CN104993124A CN201510417647.9A CN201510417647A CN104993124A CN 104993124 A CN104993124 A CN 104993124A CN 201510417647 A CN201510417647 A CN 201510417647A CN 104993124 A CN104993124 A CN 104993124A
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- 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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- 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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- H01—ELECTRIC ELEMENTS
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- 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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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Abstract
A preparation method of laminated lithium nickel manganese oxide belongs to the field of a preparation method of a lithium nickel manganese oxide anode material and shape controlling, and comprises the following steps of firstly, dissolving lithium salt and manganese salt into deionized water, and slowly dropwise adding hydrogen peroxide under the condition of stirring, so as to obtain a black solution; adding nickel salt into the solution, and carrying out sol-gel on the solution, so as to obtain a black jelly; drying and burning the jelly, so as to obtain a laminated lithium nickel manganese oxide material. The method is simple in preparation technology, and the raw materials are cheap and easy to obtain; the obtained material has a regular two-dimension laminated structure, and two-dimension laminates are arranged directionally and orderly to form a three-dimension structure, the gaps between every two adjacent layers can enlarge the effective contact area of the anode material and electrolyte, reduce the insertion/extraction resistance of a lithium ion and obviously improve the rate capability of a cell.
Description
Technical field
The present invention relates to the preparation method of layered cathode material, particularly the preparation method of laminate nickel ion doped material.
Background technology
Lithium ion battery has important application prospect in fields such as energy-storage systems.Along with the fast development of lithium ion battery for electric vehicle, people propose further requirement to the specific energy density of battery, specific power density.
Spinel-type nickel ion doped has energy density (theoretical value is 1100 Wh/kg, and actual value can be close to 700 Wh/kg) and operating voltage (electrode potential about 4.7 V, vs Li/Li
+) height, Stability Analysis of Structures, raw materials are abundant, security performance high, be high-energy-density, high power density type anode material for lithium-ion batteries contenders (see Arumugam Manthiram, Katharine Chemelewski, Eun-Sung Lee. A perspective on the high-voltage LiMn
1.5ni
0.5o
4spinel cathode for lithium-ion batteries [J]. Energy Environ. Sci., 2014,7:1339 – 1350).In recent years, the research and development of high-voltage electrolyte achieve rapid progress, make the exploitation prospect of nickel ion doped material more optimistic (see Kang Xu. Electrolytes and interphases in Li-ion batteries and beyond [J]. Chem. Rev., 2014,114:11503 – 11618).
Want the power density improving nickel ion doped material further, need, on the basis ensureing its 4.7 V operating voltage, put forth effort to improve its fast charging and discharging ability, i.e. large high rate performance.It has been generally acknowledged that the key factor of charge-discharge magnification determining lithium ion battery is lithium ion and the migration rate of electronics in electrode material, and increase ion and the dynamic (dynamical) method of electronics transmission in the battery and mainly concentrate on and seek new electrode material and design the electrode material structure that can make ion and the transmission of electronics high magnification, or nano material is used to reduce the path of electronics and lithium ion movement.At present, the difficulty of research and development new electrode materials is excessive and process cost and risk are all higher, therefore the nanometer being designed with the electrode material structure and material being beneficial to electric transmission solves battery fast charging and discharging the most frequently used method (see Jiantie Xu, Shixue Dou, Huakun Liu, et al. Cathode materials for next generation lithium ion batteries [J]. Nano Energy, 2013,2:439 – 442).
Summary of the invention
The object of this invention is to provide a kind of preparation method of laminate nickel ion doped.
The present invention is a kind of preparation method of laminate nickel ion doped material, the steps include:
(1) at room temperature, the ratio that is dissolved in by manganese salt is in the mixed liquor of the alcohol and water of 1:9-1:1, and the molar concentration of manganese ion in alcohol solution is 0.3-1.5 mol/L, in above-mentioned mixed liquor, directly add lithium salts; The consumption of manganese, lithium salts in molar ratio 3:2 is determined; Then under agitation, add to above-mentioned solution the hydrogen peroxide that molal quantity is manganese salt molal quantity 0.4-2 times, now obtain dark solution;
(2) joined by nickel salt in above-mentioned dark solution, the consumption of manganese, lithium, nickel salt in molar ratio for 3:2:1 determines, and continues stirring 1-6 h;
At (3) 70-100 DEG C, gained solution is heated, with recycling design also obtained jelly; Then by jelly dry 2-12 h at 100-120 DEG C;
(4) dried material is calcined, the nickel ion doped material with regular two-dimensional layer plate structure can be obtained.
Usefulness of the present invention is: (1) preparation method's technique is simple, and cheaper starting materials is easy to get, and is easy to promotion and implementation; Resulting materials compound with regular structure; (2) in the alcohol/water mixed liquid of manganese salt, lithium salts, add hydrogen peroxide, utilize the oxidizability of hydrogen peroxide to improve the valence state of manganese ion in advance, effectively prevent the existence of nickel ion doped material middle or low price manganese.
After being mixed into nickel salt, to utilize in alcohol/water mixed liquid the nucleation of manganese salt and the Surface Modification Effect of alcohol after pre-oxidation, both ensure that the Homogeneous phase mixing of nickel, manganese, lithium three kinds of elements, in turn ensure that the dominant growth of material on stratiform direction, and can guarantee to obtain the good plies of material of crystal property.
Accompanying drawing explanation
X x ray diffraction (XRD) collection of illustrative plates of the laminate nickel ion doped material of Fig. 1 prepared by the embodiment of the present invention 1, the laminate nickel ion doped material of Fig. 2 prepared by embodiments of the invention 1 stereoscan photograph.
Embodiment
The present invention is a kind of preparation method of laminate nickel ion doped material, the steps include:
(1) at room temperature, the ratio that is dissolved in by manganese salt is in the mixed liquor of the alcohol and water of 1:9-1:1, and the molar concentration of manganese ion in alcohol solution is 0.3-1.5 mol/L, in above-mentioned mixed liquor, directly add lithium salts; The consumption of manganese, lithium salts in molar ratio 3:2 is determined; Then under agitation, add to above-mentioned solution the hydrogen peroxide that molal quantity is manganese salt molal quantity 0.4-2 times, now obtain dark solution;
(2) joined by nickel salt in above-mentioned dark solution, the consumption of manganese, lithium, nickel salt in molar ratio for 3:2:1 determines, and continues stirring 1-6 h;
At (3) 70-100 DEG C, gained solution is heated, with recycling design also obtained jelly; Then by jelly dry 2-12 h at 100-120 DEG C;
(4) dried material is calcined, the nickel ion doped material with regular two-dimensional layer plate structure can be obtained.
Resulting materials of the present invention has regular two-dimensional layer plate structure, and two-dimentional laminate Orienting ordered arrangement forms three-dimensional structure; Gap between layers can expand effective contact area of positive electrode and electrolyte, and reduces the embedding of lithium ion/deviate from resistance, can significantly improve the large high rate performance of battery, and then promote the specific power density of battery.This preparation method's technique is simple, and cheaper starting materials is easy to get, and is easy to promotion and implementation.
According to above-described preparation method, described manganese salt is manganese sulfate, or manganese acetate, or manganese nitrate, or manganese chloride, or the mixture of one or more described arbitrary proportions; Described lithium salts is lithium sulfate, or lithium acetate, or lithium nitrate, or lithium chloride, or the mixture of one or more described arbitrary proportions; Described nickel salt is nickelous sulfate, or nickel acetate, or nickel nitrate, or nickel chloride, or the mixture of one or more described arbitrary proportions; Described alcohol is ethanol, or methyl alcohol, or the mixture of described one or both arbitrary proportion.
According to above-described preparation method, the molar concentration of manganese ion in alcohol solution is 0.3-1.5 mol/L, the consumption of manganese, nickel, lithium salts in molar ratio 3:2:1 is determined, the mixed volume of alcohol and water is than being 1:9-1:1, and the molal quantity of hydrogen peroxide used is 0.4-2 times of manganese salt molal quantity.
According to above-described preparation method, calcining heat is 600-850 DEG C, and calcination time is 8-12 h.
Embodiment 1:
(1) by 0.3 mol manganese sulfate, 0.2 mol lithium sulfate is dissolved in (volume ratio of alcohol and water is 3:9) in the mixed liquor of 1 L second alcohol and water;
(2) add 0.12 mol(24 wt%) hydrogen peroxide, then add 0.1 mol nickel acetate, and Keep agitation 3 h;
At (3) 90 DEG C, gained solution is heated, with recycling design also obtained jelly.Then jelly is placed in dry 8 h of baking oven of 120 DEG C;
(4) last, dried material is calcined 8 h at 800 DEG C in Muffle furnace, the laminate nickel ion doped material as shown in accompanying drawing 1,2 can be obtained.
Embodiment 2:
(1) by 0.9 mol manganese acetate, 0.6mol lithium acetate is dissolved in (volume ratio of alcohol and water is 1:9) in the mixed liquor of 1 L second alcohol and water;
(2) add 0.45 mol(24 wt%) hydrogen peroxide, then add 0.3 mol nickel acetate, and Keep agitation 3 h;
At (3) 100 DEG C, gained solution is heated, with recycling design also obtained jelly.Then jelly is placed in dry 8 h of baking oven of 120 DEG C;
(4) last, dried material is calcined 9 h at 850 DEG C in Muffle furnace, laminate nickel ion doped material can be obtained.
Embodiment 3:
(1) by 1.5mol manganese acetate, 1mol lithium acetate is dissolved in (volume ratio of alcohol and water is 2:9) in the mixed liquor of 1 L second alcohol and water;
(2) add 0.6 mol(24 wt%) hydrogen peroxide, then add 0.5 mol nickel acetate, and Keep agitation 3 h;
At (3) 100 DEG C, gained solution is heated, with recycling design also obtained jelly.Then jelly is placed in dry 8 h of baking oven of 120 DEG C;
(4) last, dried material is calcined 10 h at 850 DEG C in Muffle furnace, laminate nickel ion doped material can be obtained.
Claims (4)
1. a preparation method for laminate nickel ion doped material, is characterized in that, the steps include:
(1) at room temperature, the ratio that is dissolved in by manganese salt is in the mixed liquor of the alcohol and water of 1:9-1:1, and the molar concentration of manganese ion in alcohol solution is 0.3-1.5 mol/L, in above-mentioned mixed liquor, directly add lithium salts; The consumption of manganese, lithium salts in molar ratio 3:2 is determined; Then under agitation, add to above-mentioned solution the hydrogen peroxide that molal quantity is manganese salt molal quantity 0.4-2 times, now obtain dark solution;
(2) joined by nickel salt in above-mentioned dark solution, the consumption of manganese, lithium, nickel salt in molar ratio for 3:2:1 determines, and continues stirring 1-6 h;
At (3) 70-100 DEG C, gained solution is heated, with recycling design also obtained jelly; Then by jelly dry 2-12 h at 100-120 DEG C;
(4) dried material is calcined, the nickel ion doped material with regular two-dimensional layer plate structure can be obtained.
2. the preparation method of laminate nickel ion doped material according to claim 1, is characterized in that: described manganese salt is manganese sulfate, or manganese acetate, or manganese nitrate, or manganese chloride, or the mixture of one or more described arbitrary proportions; Described lithium salts is lithium sulfate, or lithium acetate, or lithium nitrate, or lithium chloride, or the mixture of one or more described arbitrary proportions; Described nickel salt is nickelous sulfate, or nickel acetate, or nickel nitrate, or nickel chloride, or the mixture of one or more described arbitrary proportions; Described alcohol is ethanol, or methyl alcohol, or the mixture of described one or both arbitrary proportion.
3. the preparation method of laminate nickel ion doped material according to claim 1, it is characterized in that: the molar concentration of manganese ion in alcohol solution is 0.3-1.5 mol/L, the consumption of manganese, nickel, lithium salts in molar ratio 3:2:1 is determined, alcohol is 1:9-1:1 with the mixed volume ratio of water, and the molal quantity of hydrogen peroxide used is 0.4-2 times of manganese salt molal quantity.
4. the preparation method of laminate nickel ion doped material according to claim 1, it is characterized in that: calcining heat is 600-850 DEG C, calcination time is 8-12 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675359A (en) * | 2018-05-22 | 2018-10-19 | 兰州理工大学 | A kind of preparation method of high-voltage lithium ion batteries nickel lithium manganate cathode material |
Citations (4)
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| CN1372340A (en) * | 2001-05-30 | 2002-10-02 | 中国科学院青海盐湖研究所 | Positive pole material of lithium ion cell and preparation method thereof |
| CN102249341A (en) * | 2010-11-04 | 2011-11-23 | 耿世达 | Manufacturing method for layered lithium manganate cathode material for lithium ion battery |
| CN103280570A (en) * | 2013-05-23 | 2013-09-04 | 上海中聚佳华电池科技有限公司 | Preparation method of micron-order single-crystal nickel lithium manganate anode material |
| CN103985854A (en) * | 2014-04-14 | 2014-08-13 | 江苏中欧材料研究院有限公司 | Preparation method of nanoscale nickel lithium manganate positive pole material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1372340A (en) * | 2001-05-30 | 2002-10-02 | 中国科学院青海盐湖研究所 | Positive pole material of lithium ion cell and preparation method thereof |
| CN102249341A (en) * | 2010-11-04 | 2011-11-23 | 耿世达 | Manufacturing method for layered lithium manganate cathode material for lithium ion battery |
| CN103280570A (en) * | 2013-05-23 | 2013-09-04 | 上海中聚佳华电池科技有限公司 | Preparation method of micron-order single-crystal nickel lithium manganate anode material |
| CN103985854A (en) * | 2014-04-14 | 2014-08-13 | 江苏中欧材料研究院有限公司 | Preparation method of nanoscale nickel lithium manganate positive pole material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675359A (en) * | 2018-05-22 | 2018-10-19 | 兰州理工大学 | A kind of preparation method of high-voltage lithium ion batteries nickel lithium manganate cathode material |
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