CN103579610B - The preparation method of lithium ion battery anode material nickel LiMn2O4 - Google Patents
The preparation method of lithium ion battery anode material nickel LiMn2O4 Download PDFInfo
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- CN103579610B CN103579610B CN201310586472.5A CN201310586472A CN103579610B CN 103579610 B CN103579610 B CN 103579610B CN 201310586472 A CN201310586472 A CN 201310586472A CN 103579610 B CN103579610 B CN 103579610B
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- nickel
- hydroxide
- precipitation reagent
- lithium
- oxalate
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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 discloses the preparation method of lithium ion battery anode material nickel LiMn2O4.The method adopts oxalates and hydroxide simultaneously as precipitation reagent, prepares nickel ion doped by coprecipitation and solid sintering technology.The present invention adopts two precipitation reagent synthesis nickel ion doped presoma to be that to utilize the concentration of manganese oxalate and nickel hydroxide to amass close, by controlling the pH value of reaction solution, synthesis of oxalic acid manganese/nickel hydroxide composite precursor material, then synthesize positive electrode nickel ion doped by sintering after mixing with lithium source.Present invention eliminates and adopt only hydroxide to be the step that precipitation reagent needs inert gas shielding, reduce production cost; Compared with the nickel ion doped only using oxalates to prepare for precipitation reagent, tap density is effectively improved; Because the solubility product of manganese oxalate and nickel hydroxide is close, thus according to the control of solution ph, more uniform manganese oxalate/nickel hydroxide persursor material can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery anode material nickel LiMn2O4.
Background technology
Along with the development of society, China's energy crisis and environmental pollution day by day serious, exploitation and the research of electrokinetic cell receive much concern.Lithium ion battery is a kind of high-energy battery that fast development is nearly ten years got up, and no matter from technical indicators such as life-span, specific energy and voltages, or from environment, it has become an important directions of China's New Energy Industry.Positive electrode nickel ion doped has that discharge voltage is high, Heat stability is good and the advantage such as price is lower, is considered to most potential positive electrode material.The precipitation reagent of current use Co deposited synthesis nickel ion doped material precursor mostly is oxalates, hydroxide, carbonate etc.The tap density of the nickel ion doped material adopting oxalates or carbonate to synthesize as precipitation reagent is lower, thus energy density in electrokinetic cell is less; And although the nickel ion doped material tap density adopting hydroxide to synthesize as precipitation reagent is higher, need the protection of inert gas, also higher to the requirement of equipment.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of lithium ion battery anode material nickel LiMn2O4, i.e. two precipitation reagent coprecipitation.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of lithium ion battery anode material nickel LiMn2O4, comprises the following steps:
(1) with the acetate of nickel, manganese, nitrate or sulfate for transition metal source, be n (Ni): n (Mn)=1:1 ~ 3 according to mol ratio; Precise material, adds the mixing salt solution A that appropriate distilled water makes nickel, manganese;
(2) using sodium oxalate, potassium oxalate or ammonium oxalate as a kind of precipitation reagent, and using NaOH or potassium hydroxide as another kind of precipitation reagent, be n (C in molar ratio
2o
4 2-): n (OH
-)=0.5 ~ 2:1 configures precipitant solution B;
(3) added by mixing salt solution A and precipitant solution B simultaneously and fill in the container of distilled water, low whipping speed is under the condition of 200 ~ 800r/min, and by controlling the speed adding precipitation reagent, the pH value regulating reactant liquor is 8.5 ~ 10.5; In whole course of reaction, the temperature of reactant liquor is 25 ~ 80 DEG C, reacts washing after 0.5 ~ 6 hour, drying, obtains the presoma of manganese oxalate/nickel hydroxide;
(4) presoma that step (3) obtains is placed in pre-burning 4 ~ 7h under the environment of 400 ~ 600 DEG C, be that n (Li): n (Ni+Mn)=1.05 ~ 2.10:2 mix with lithium nitrate, lithium carbonate, lithium hydroxide or lithium acetate according to mol ratio by the product after pre-burning, obtain mixture;
(5) mixture of step (4) is calcined 6 ~ 18h at 750 ~ 1000 DEG C, then at 600 ~ 750 DEG C of annealing in process 4 ~ 14h, obtain lithium ion battery anode material nickel LiMn2O4.
The invention has the beneficial effects as follows:
(1) because the solubility product of manganese oxalate and nickel hydroxide is close, 1.1 × 10 are respectively
-15mol/L and 2.0 × 10
-15mol/L; And the solubility product of manganous hydroxide and nickel oxalate is relatively large, be respectively 1.9 × 10
-13mol/L and 4.0 × 10
-10mol/L.By controlling the pH value of solution, prepare nickel hydroxide/manganese oxalate composite precursor, thus eliminate and adopt only hydroxide to be the step that precipitation reagent needs inert gas shielding, reduce production cost;
(2) compared with the nickel ion doped only using oxalates to prepare for precipitation reagent, tap density is effectively improved; Because the solubility product of manganese oxalate and nickel hydroxide is close, thus according to the control of solution ph, more uniform manganese oxalate/nickel hydroxide persursor material can be obtained.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is the charging and discharging curve that the synthetic spinel nickel ion doped of the embodiment of the present invention 1 and lithium metal form simulated battery.
Fig. 2 is the charging and discharging curve that the embodiment of the present invention 2-in-1 one-tenth spinel nickel LiMn2O4 and lithium metal form simulated battery.
Embodiment
Embodiment 1:
(1) n (Ni): n (Mn)=1:3 in molar ratio, precise manganese sulfate, nickelous sulfate, add appropriate distilled water and be configured to mixed solution A.
(2) be that 1.5:1 configures precipitant solution B by the mol ratio of sodium oxalate and NaOH.
(3) mixing salt solution A and precipitant solution B added to containing in the container of distilled water, low whipping speed is under the condition of 300r/min simultaneously, by controlling to add pH value in the speed adjustment reactant liquor of precipitation reagent about 9.5.In whole course of reaction, the temperature of reactant liquor is 40 DEG C, reacts washing after 3 hours, drying, obtains the presoma of manganese oxalate/nickel hydroxide.
(4) presoma that step (3) obtains is placed in pre-burning 6h under the environment of 500 DEG C, is that n (Li): n (Ni+Mn)=1.05:2 mixes by the product lithium carbonate after pre-burning according to mol ratio, obtains mixture.
(5) mixture step (4) obtained, at 800 DEG C of calcining 7h, then at 700 DEG C of annealing in process 10h, obtains the lithium ion battery anode material nickel LiMn2O4 with good spinel structure.
Embodiment 2:
(1) n (Ni): n (Mn)=1:3 in molar ratio, precise manganese sulfate, nickelous sulfate, add appropriate distilled water and be configured to mixed solution A.
(2) be that 1.5:1 configures precipitant solution B by the mol ratio of potassium oxalate and NaOH.
(3) mixing salt solution A and precipitant solution B added to containing in the container of distilled water, low whipping speed is under the condition of 300r/min simultaneously, by controlling to add pH value in the speed adjustment reactant liquor of precipitation reagent about 9.3.In whole course of reaction, the temperature of reactant liquor, at 50 DEG C, is reacted washing after 3 hours, drying, is obtained the presoma of manganese oxalate/nickel hydroxide.
(4) presoma that step (3) obtains is placed in pre-burning 6h under the environment of 500 DEG C, is that n (Li): n (Ni+Mn)=1.05:2 mix with lithium carbonate according to mol ratio by the product after pre-burning, obtains mixture.
(5) mixture step (4) obtained is at 800 DEG C of calcining 7h, and then 700 DEG C of annealing in process 10h, obtains the lithium ion battery anode material nickel LiMn2O4 with good spinel structure.
Embodiment 3:
(1) n (Ni): n (Mn)=1:3 in molar ratio, precise manganese sulfate, nickelous sulfate, add appropriate distilled water and be configured to mixed solution A;
(2) be n (C in molar ratio
2o
4 2-): n (OH
-)=1.5:1 configures potassium oxalate, ammonium oxalate and potassium hydroxide precipitant solution B, wherein n (potassium oxalate): n (ammonium oxalate)=2:1;
(3) mixing salt solution A and precipitant solution B added to containing in the container of distilled water, low whipping speed is under the condition of 300r/min simultaneously, by controlling to add pH value in the speed adjustment reactant liquor of precipitation reagent about 9.8.In addition, in whole course of reaction, the temperature of reactant liquor, at 50 DEG C, is reacted washing after 3 hours, drying, is obtained the presoma of manganese oxalate/nickel hydroxide;
(4) presoma that step (3) obtains is placed in pre-burning 6h under the environment of 600 DEG C, be that n (Li): n (Ni+Mn)=1.05:2 mix with lithium carbonate according to mol ratio by the product after pre-burning, obtain the mixture mixed;
(5) mixture step (4) obtained, at 800 DEG C of calcining 7h, then at 700 DEG C of annealing in process 10h, obtains the lithium ion battery anode material nickel LiMn2O4 with good spinel structure.
Embodiment 4:
(1) n (Ni): n (Mn)=1:1 in molar ratio, precise manganese sulfate, nickelous sulfate, add appropriate distilled water and be configured to mixed solution A;
(2) be n (C in molar ratio
2o
4 2-): n (OH
-)=0.5:1 configures potassium oxalate and potassium hydroxide precipitant solution B;
(3) mixing salt solution A and precipitant solution B added to containing in the container of distilled water, low whipping speed is under the condition of 300r/min simultaneously, by controlling to add pH value in the speed adjustment reactant liquor of precipitation reagent about 9.3.In addition, in whole course of reaction, the temperature of reactant liquor, at 50 DEG C, is reacted washing after 3 hours, drying, is obtained the presoma of manganese oxalate/nickel hydroxide; .
(4) presoma that step (3) obtains is placed in pre-burning 7h under the environment of 500 DEG C, be that n (Li): n (Ni+Mn)=1.05:1 mix with lithium carbonate according to mol ratio by the product after pre-burning, obtain the mixture mixed;
(5) mixture step (4) obtained, at 950 DEG C of calcining 10h, then at 700 DEG C of annealing in process 10h, obtains the lithium ion battery anode material nickel LiMn2O4 with layer structure.
Embodiment 5:
The present embodiment and embodiment 3 difference are: the pH value in step (3) controls about 10.5, and the sintering temperature in step (5) is the sintering time in 1000 DEG C and step (5) is 6h.
Embodiment 6:
The present embodiment and embodiment 2 difference are: the pH value in step (3) controls about 8.5, and the sintering temperature in step (5) is 750 DEG C.Sintering time in step (5) is 18h, and the annealing conditions in step (5) is 600 DEG C of calcining 4h.
The nickel ion doped material of gained in above-described embodiment 1 and embodiment 2 is assembled into button cell respectively, in battery, positive electrode ratio is nickel ion doped: conductive agent: binding agent=80:10:10, adopt Clgard2300 type barrier film, be metal lithium sheet to electrode, carry out charge-discharge performance test with 0.2C, charging/discharging voltage scope is 3.0-4.3V.The sample that embodiment 1 obtains after tested after charging and discharging curve as shown in Figure 1, the sample that embodiment 2 obtains after tested after charging and discharging curve as shown in Figure 2.As can be seen from charging and discharging curve, present charge and discharge platform at about 4.7V, illustrate that the material of synthesis is spinel nickel lithium manganate material.
Above-described embodiment of the present invention, does not form limiting the scope of the present invention.Any amendment done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within claims of the present invention.
Claims (1)
1. the preparation method of lithium ion battery anode material nickel LiMn2O4, is characterized in that comprising the following steps:
(1) with the acetate of nickel, manganese, nitrate or sulfate for transition metal source, be n (Ni): n (Mn)=1:1 ~ 3 according to mol ratio; Precise material, adds the mixing salt solution A that appropriate distilled water makes nickel, manganese;
(2) using sodium oxalate, potassium oxalate or ammonium oxalate as a kind of precipitation reagent, and using NaOH or potassium hydroxide as another kind of precipitation reagent, be n (C in molar ratio
2o
4 2-): n (OH
-)=0.5 ~ 2:1 configures precipitant solution B;
(3) added by mixing salt solution A and precipitant solution B simultaneously and fill in the container of distilled water, low whipping speed is under the condition of 200 ~ 800r/min, and by controlling the speed adding precipitation reagent, the pH value regulating reactant liquor is 8.5 ~ 10.5; In whole course of reaction, the temperature of reactant liquor is 25 ~ 80 DEG C, reacts washing after 0.5 ~ 6 hour, drying, obtains the presoma of manganese oxalate/nickel hydroxide;
(4) presoma that step (3) obtains is placed in pre-burning 4 ~ 7h under the environment of 400 ~ 600 DEG C, be that n (Li): n (Ni+Mn)=1.05 ~ 2.10:2 mix with lithium nitrate, lithium carbonate, lithium hydroxide or lithium acetate according to mol ratio by the product after pre-burning, obtain mixture;
(5) mixture of step (4) is calcined 6 ~ 18h at 750 ~ 1000 DEG C, then at 600 ~ 750 DEG C of annealing in process 4 ~ 14h, obtain lithium ion battery anode material nickel LiMn2O4.
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| CN106684350B (en) * | 2016-12-21 | 2020-01-07 | 桑顿新能源科技有限公司 | Preparation method of high-voltage positive electrode material lithium nickel manganese oxide |
| CN108288711A (en) * | 2018-02-12 | 2018-07-17 | 成都理工大学 | A kind of quaternary lithium-ion battery positive electrode material and preparation method |
| CN109811412B (en) * | 2018-12-28 | 2021-06-11 | 广东邦普循环科技有限公司 | Single-crystal-shaped layered lithium nickel manganese oxide positive electrode material and preparation method thereof |
| CN110137445A (en) * | 2019-03-26 | 2019-08-16 | 广西卓能新能源科技有限公司 | Battery anode slice, lithium ion battery, stratiform nickel ion doped and preparation method thereof |
| CN114408987B (en) * | 2022-03-30 | 2022-06-21 | 宜宾锂宝新材料有限公司 | Nickel-cobalt-manganese precursor, ternary cathode material and preparation method thereof |
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| CN102034967A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery |
| CN103107328A (en) * | 2013-01-25 | 2013-05-15 | 湖南桑顿新能源有限公司 | Preparation method of modified spinel type lithium manganate |
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| US8277683B2 (en) * | 2008-05-30 | 2012-10-02 | Uchicago Argonne, Llc | Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries |
| CN103119773A (en) * | 2010-03-19 | 2013-05-22 | 第一工业制药株式会社 | Lithium secondary battery using ionic liquid |
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| CN102034967A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery |
| CN103107328A (en) * | 2013-01-25 | 2013-05-15 | 湖南桑顿新能源有限公司 | Preparation method of modified spinel type lithium manganate |
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Application publication date: 20140212 Assignee: NANJING GUOXUAN BATTERY CO., LTD. Assignor: Hefei Guoxuan High-Tech Power Energy Co., Ltd. Contract record no.: 2017320000046 Denomination of invention: Method for preparing nickel lithium manganate serving as cathode material of lithium ion battery Granted publication date: 20160330 License type: Exclusive License Record date: 20170306 |