CN1171826C - Method of synthesizing positive pole material for lithium ion battery - Google Patents
Method of synthesizing positive pole material for lithium ion battery Download PDFInfo
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- CN1171826C CN1171826C CNB99115147XA CN99115147A CN1171826C CN 1171826 C CN1171826 C CN 1171826C CN B99115147X A CNB99115147X A CN B99115147XA CN 99115147 A CN99115147 A CN 99115147A CN 1171826 C CN1171826 C CN 1171826C
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- lithium
- manganese
- battery
- positive electrode
- oxygenant
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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 belongs to a novel synthesizing method of metal composite oxide, which is a method particularly to suitable for synthesizing composite oxide form metals with varying valences, and is particularly suitable for the positive electrode materials of a lithium (ion) battery and composite oxide catalysts. The purpose of the present invention is to provide a simple, practical and novel material synthesizing method whose industrialization is easy to realize, thereby achieving the purposes of energy conservation, production efficiency increase and environmental pollution reduction. The present invention is characterized in that a compound containing lithium is dissolved in mixed solution containing oxidant and precipitant; when the mixed solution with the compound containing lithium is strongly agitated, the solution is added to the solution of a compound containing manganese, so in-situ redox precipitation happens to the solution containing lithium. The precipitated material is processed by aging for 1 to 12h, distilled to dry, baked for more than a night (12h) at a temperature of 105 to 125DEG C, ground and roasted in air for 6 to 24h at a temperature of 600 to 800DEG C. A sample which has the material composition of Li<x>Mn<2-y>M'yO4 (0<x<=2, 0<=y<=1) is obtained. The sample presents a spinel structure and has good electrochemical property, the sample can charge and discharge with a constant current under the condition of 0.2 to 0.5C, the discharge specific capacity of the first time is larger than 110 mAh/g, and the efficiency is larger than 90%; after circulations for 100 times, the discharge specific capacity is still larger than 105 mAh/g, and the efficiency is larger than 95%. The material has good stability, simple preparation and good repeatability.
Description
The invention belongs to technical field of material, particularly positive electrode material synthetic technical field in lithium (ion) battery.Certainly the technical field that also comprises the preparation of metal (especially variable valency metal) composite oxides and metal composite oxide catalyst.
Lithium ion battery is the high-energy density secondary battery that the early 1990s in this century is just taken the lead in developing by Japanese Sony company.It has monomer battery voltage height (3.6 volts of nominal voltages), the energy density height, and specific energy is big, and volume is little, and is in light weight, has extended cycle life, and self-discharge rate is low, characteristics such as memory-less effect.Be particularly suitable for doing mobile telephone, laptop computer is taken the photograph the energy of videocorder and electromobile etc.
As the transition metal oxide of lithium (ion) cell positive material, as LiCoO
2, LiNiO
2, LiMnO
2And LiMn
2O
4, its traditional synthetic method is a solid reaction process.Normally with compound (alkali or salt) that contains lithium and the oxide compound that contains transition metal, oxyhydroxide or salt are starting raw material, long-time roasting under 700～1000 ℃ of high temperature, and step repetition gets for several times.The electrochemical reversible capacity of prepared thus positive electrode material is between 110～130mAh/g.Described as following reference.
1.Hayashi?N，Ikuta?H，Wakihara?M.J?Electrochem.Soc.，1999，146(4)：1351
2.Tarascon?J?M，Wang?E，Shokoohi?F?K，et?al.J?Electrochem.Soc.，1991，138(10)：2859
3.Cras?F?L，Bloch?D，Anne?M，Strobel?P.Solid?State?Ionics，1996，89：203
Because solid state reaction temperature height, constant temperature time is long, need repeatedly repeat to grind, and causes following shortcoming.(1) energy consumption height, production efficiency is low, the product cost height.(2) the lithium salts volatilization is serious under the high temperature, causes lithium to lose in a large number.(3) material particle size is bigger, lack of homogeneity.(4) introduce impurity easily, product is impure.(5) prescription is difficult to control, and product performance are difficult to stablize.
Aim of the present invention is to overcome the shortcoming and defect of above-mentioned prior art.Purpose is for save energy, enhances productivity, and guarantees the stability and the premium properties of material.
The present invention also aims to reduce the loss of lithium in the preparation process, prescription is accurately controlled, thereby made the granularity of material moderate, good uniformity, stable performance, and allow big electric current rapid discharge.
The object of the present invention is achieved like this.A kind of compound that contains lithium is dissolved in a kind of mixing solutions that contains oxygenant and precipitation agent, under brute force stirs, the above-mentioned mixing solutions that contains lithium is joined in a kind of manganiferous compound solution then, make it that in-situ oxidation precipitate reduction take place and react.Adding finishes, and continues powerful the stirring.Precipitation obtains a kind colloidal mixture through aging 1～12h.Evaporate to dryness spends the night (12h) 105～125 ℃ of oven dry then, grinds roasting 6～24h in 600～800 ℃ of air.Promptly obtain material and consist of Li
xMn
2-yM '
yO
4The sample of (0＜x≤2,0≤y≤1).The compound that contains lithium comprises: Lithium Acetate, lithium nitrate, lithium hydroxide, lithium halide etc.Manganiferous compound comprises: manganese acetate, manganous nitrate etc.Oxygenant comprises alkali metal peroxide, organo-peroxide and hydrogen peroxide and air (oxygen) etc.Precipitation agent comprises ammoniacal liquor, urea, lithium hydroxide, volatile salt, bicarbonate of ammonia and alkaline carbonate etc.
Principle of the present invention is: after manganiferous compound is water-soluble, produce divalent manganesetion Mn
2+, Mn
2+Under the alkaline precipitating agent effect, generate the Mn (OH) of white
2Precipitation.Generating Mn (OH)
2In the sedimentary process, generate brown MnOOH and MnO (OH) with the oxygenant effect in position immediately to black
2Precipitation.In the precipitation conversion process, the Li in the solution
+Be adsorbed on the precipitation, and then carry out original position and combine, because original position molecular reaction activity is very high, so Li with the precipitation molecule
+To form the mixture of product or formation molecular level with the in-situ precipitate molecular reaction.In evaporation and drying course, Li
+On molecular level, combine together fully with manganiferous precipitation.Thereby make lithium and manganese very approaching and even.So reduce Li in the thermal response greatly
+The evolving path, reduced the activation energy of diffusion, thereby caused roasting time to shorten and the maturing temperature reduction.
The invention has the advantages that and adopt in-situ oxidation precipitate reduction technology synthesis of anode material of lithium-ion battery or metal composite oxide catalyst, it is short to have preparation route and flow process, with short production cycle, the preparation method is simple and easy to do, the quality height of product, performance is good and stable, and the preparing product cost is low, the lithium loss can be ignored, the easy control of prescription etc.The chemical property of the material of preparation is good, and the specific discharge capacity height has extended cycle life, can high-multiplying power discharge.
In order better to illustrate scientific meaning of the present invention, the present invention is described in detail below in conjunction with embodiment and accompanying drawing and subordinate list.
With the manganous nitrate is the manganese source, and lithium hydroxide is the lithium source, and ammoniacal liquor and lithium hydroxide are precipitation agent jointly, and hydrogen peroxide is an oxygenant, and lithium/manganese mol ratio is 1: 2.Lithium hydroxide is dissolved in is mixed with lithium hydroxide solution in the distilled water, then 30% hydrogen peroxide is joined in the lithium hydroxide solution by a certain percentage, be mixed with mixing solutions.Under brute force stirs, again this mixing solutions is added in the manganese nitrate solution then, the reaction of in-situ oxidation precipitate reduction takes place, generate dark-brown to black glue or flocks.Continue powerful the stirring 2～6 hours behind reinforced the finishing again, pH is 8～9.Precipitation is through aging 1～12 hour, is evaporated to driedly, and 105～125 ℃ of oven dry 12 hours are ground, roasting 6～24 hours in 600～800 ℃ of following air again.The sample of preparation is the spinel structure (see figure 1) and has good electrochemical properties.As positive electrode material, acetylene black is conductive agent, and ptfe emulsion is a caking agent, is that current collector carries out smear with the aluminium foil.With the metal lithium sheet counter electrode then, with 1.0mol/L LiClO
4/ EC+DEC (1: 1Vol.) be electrolytic solution, constant current charge-discharge under 0.2～0.5C condition, the first discharge specific capacity of 750 ℃ of roasting samples is greater than 110mAh/g, efficient is greater than 90%, circulate after 100 times, still greater than the 105mAh/g (see figure 2), efficient is greater than 95% for specific discharge capacity.
With the manganese acetate is the manganese source, and lithium hydroxide is the lithium source, and ammoniacal liquor and lithium hydroxide are precipitation agent jointly, and hydrogen peroxide is an oxygenant, and lithium/manganese mol ratio is 1: 2.Step is with embodiment 1 later on.The specimen material good stability of preparation, constant current charge-discharge under 0.2～0.5C condition, the first discharge specific capacity of 750 ℃ of roasting samples is greater than 110mAh/g, and efficient is greater than 90%, circulates after 40 times, and specific discharge capacity is still greater than 105mAh/g, and efficient is greater than 95%.
Embodiment 3
With the manganous nitrate is the manganese source, and lithium nitrate is the lithium source, and ammoniacal liquor is precipitation agent, and hydrogen peroxide is an oxygenant, and lithium/manganese mol ratio is 1: 2.Step is with embodiment 1 later on.The specimen material good stability of preparation, constant current charge-discharge under 0.2～0.5C condition, the first discharge specific capacity of 750 ℃ of roasting samples is greater than 110mAh/g, and efficient is greater than 90%, circulates after 40 times, and specific discharge capacity is still greater than 105mAh/g, and efficient is greater than 95%.
Embodiment 4
With the manganese acetate is the manganese source, and lithium nitrate is the lithium source, and ammoniacal liquor is precipitation agent, and hydrogen peroxide is an oxygenant, and lithium/manganese mol ratio is 1: 2.Step is with embodiment 1 later on.The specimen material good stability of preparation, constant current charge-discharge under 0.2～0.5C condition, the first discharge specific capacity of 750 ℃ of roasting samples is greater than 110mAh/g, and efficient is greater than 90%, circulates after 30 times, and specific discharge capacity is still greater than 105mAh/g, and efficient is greater than 95%.
Embodiment 5
Present embodiment is investigated lithium/manganese mol ratio to material first charge-discharge Effect on Performance.Except that lithium/manganese mol ratio difference, other preparation conditions are with embodiment 1.
Table 1 lithium/manganese mol ratio is to material first charge-discharge Effect on Performance
Lithium/manganese mol ratio specific volume initial charge specific volume first charge-discharge that discharges is first imitated
The amount dose rate
(mAh/g) (mAh/g) (％)
0.90/2 112.30 123.70 90.8
0.95/2 112.10 125.00 89.7
1.00/2 115.70 128.40 90.1
1.05/2 113.40 128.30 88.4
1.10/2 113.30 129.70 87.4
1.15/2 112.10 129.10 86.9
1.20/2 111.80 128.30 87.1
Embodiment 6
Present embodiment is investigated the influence of maturing temperature to material electrochemical performance.Except that the maturing temperature difference, other preparation conditions and step are with embodiment 1.
Table 2 maturing temperature is to the influence of material electrochemical performance
The maturing temperature specific volume initial charge specific volume first charge-discharge that discharges is first imitated
(℃) amount (mAb/g) amount (mAh/g) rate (%)
600 100.30 132.60 75.6
650 108.30 129.80 83.5
700 113.80 128.70 88.4
750 115.70 128.40 90.1
800 115.60 125.30 92.3
Embodiment 7
In embodiment 1～6, the electro-chemical test condition of material also comprises: positive electrode material (active substance) content is 75～90%, and conductive agent (acetylene black) content is 5～20%, and (tetrafluoroethylene, PTFE) content is 2～10% to caking agent.Be weight ratio.After positive active material and conductive agent and caking agent three be mixed in proportion, grind evenly in agate mortar, (10～30um) is that current collector carries out the roll extrusion smear with aluminium foil then.
Claims (3)
1, the novel method of positive electrode material in a kind of synthetic lithium (ion) battery is characterized in that: a kind of compound that contains lithium is dissolved in a kind of mixing solutions that contains oxygenant and precipitation agent, forms mixing solutions; Under brute force stirs, this mixing solutions joined then in a kind of solution that contains manganic compound, make it that reaction of in-situ oxidation precipitate reduction take place; Behind the in-situ oxidation precipitate reduction, precipitation is through aging 1-12 hour, evaporate to dryness then, and 105-125 ℃ of oven dry ground, in the 600-800 ℃ of air roasting 6-24 hour; Take out behind the furnace cooling, promptly get material, material is spinel structure, and wherein said lithium-containing compound is Lithium Acetate, lithium nitrate, lithium hydroxide or lithium halide; The described manganic compound that contains is manganese acetate or manganous nitrate; Described oxygenant is alkali metal peroxide, organo-peroxide, hydrogen peroxide or air; Described precipitation agent is urea, ammoniacal liquor, lithium hydroxide, volatile salt, bicarbonate of ammonia or alkaline carbonate; Described material consist of Li
xMn
2-yM
yO
4, wherein: 0＜X≤2,0≤y≤1, M is Co, Ni, Mn, Cr or Al, the molar ratio of described oxygenant and manganese is 0.1-2.0: 1.0.
2, according to the novel method of positive electrode material in the described synthetic lithium of claim 1 (ion) battery, it is characterized in that: described drying time is 12 hours.
3, according to the novel method of positive electrode material in the described synthetic lithium of claim 1 (ion) battery, it is characterized in that: the molar ratio of described oxygenant and manganese is 0.5-1.2: 1.0.
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|---|---|---|---|
| CNB99115147XA CN1171826C (en) | 1999-09-22 | 1999-09-22 | Method of synthesizing positive pole material for lithium ion battery |
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|---|---|---|---|
| CNB99115147XA CN1171826C (en) | 1999-09-22 | 1999-09-22 | Method of synthesizing positive pole material for lithium ion battery |
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| CN1171826C true CN1171826C (en) | 2004-10-20 |
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| CNB99115147XA Expired - Fee Related CN1171826C (en) | 1999-09-22 | 1999-09-22 | Method of synthesizing positive pole material for lithium ion battery |
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| KR20120061909A (en) * | 2009-12-27 | 2012-06-13 | 구이저우 젠후아 뉴 머티어리얼 컴퍼니, 엘티디. | High manganese polycrystalline anode material, preparation method thereof and dynamic lithium ion battery |
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1999
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