CN103715415B - The preparation method of manganate cathode material for lithium - Google Patents
The preparation method of manganate cathode material for lithium Download PDFInfo
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- CN103715415B CN103715415B CN201310729306.6A CN201310729306A CN103715415B CN 103715415 B CN103715415 B CN 103715415B CN 201310729306 A CN201310729306 A CN 201310729306A CN 103715415 B CN103715415 B CN 103715415B
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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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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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- H—ELECTRICITY
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- 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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- 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
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Abstract
The invention discloses a kind of preparation method of manganate cathode material for lithium, comprise the following steps: (1) preparation mixing salt solution; (2) precipitant solution is prepared; (3) salting liquid and precipitant solution time are slowly squeezed in reactor in pH=7 ~ 13; (4) take manganese dioxide in proportion, and added in the mixed liquor that step (3) obtains, continue to stir, ageing 5 ~ 20h, then by solid-liquid product separately, with deionized water by the washing of gained presoma to alkalescent; (5) join in ball grinder by the presoma behind lithium source and washing, ball milling 2 ~ 5h, then 80 ~ 120 DEG C of oven dry, obtains persursor material; (6) gained persursor material is carried out double roasting respectively, sintering resulting materials is carried out fragmentation, screening, obtain described manganate cathode material for lithium.This method is simple, and prepared lithium manganate material capacity is high, has excellent high temperature cyclic performance.
Description
Technical field
The present invention relates to lithium rechargeable battery, be specifically related to a kind of preparation method of manganate cathode material for lithium.
Background technology
Lithium rechargeable battery because of its have energy density high, have extended cycle life, the advantage such as self-discharge rate is little and be widely used in portable type electronic product, electric vehicle, recharging and the field such as energy storage and Aero-Space.The performance of lithium ion battery depends on positive electrode to a great extent, and at present, it is several that conventional anode material for lithium-ion batteries mainly contains cobalt acid lithium, ternary material, LiFePO4 etc.Specific energy is high owing to having for cobalt acid lithium, electric discharge steadily, the advantage such as high, the good cycle of operating voltage, now be widely used in the positive electrode part of commercial li-ion battery, but due to cobalt resource lack, expensive and seriously polluted to environment, limit its development.And lithium manganate material have fail safe good, nontoxic, pollute little, aboundresources, the advantage such as with low cost becomes one of positive electrode being expected to the lithium ion battery replacing cobalt acid lithium material, has good application prospect.But the capacity low and high temperature of lithium manganate material 55 DEG C of cycle performances difference and microscopic appearance is poor etc. that shortcoming limits its development.
The method that tradition prepares LiMn2O4 has two kinds, is mainly reflected on mixing method.One is solid phase method: adopt mixing oxides method to mix manganese source, lithium source and doped chemical, after through roasting, the techniques such as pulverizing prepare lithium manganate material, this method due to batch mixing uneven, cause synthetic material composition inequality, particle size distribution is wide, form is uneven, have impact on physical and chemical performance and the chemical property of battery material.Another kind is liquid phase method: by manganese source, lithium source and doped chemical using ethanol equal solvent as dispersant, adopts liquid phase ball-milling method to be mixed by raw material, and this kind of mode, owing to adopting organic solvent as dispersant, is not easy to suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of uniform composition, manganate cathode material for lithium that high temperature cyclic performance is good.
For this reason, technical scheme of the present invention is as follows:
A preparation method for manganate cathode material for lithium, the molecular formula of described manganate cathode material for lithium is LiMn
xco
ycr
zo
4, wherein x=1.88 ~ 1.96, x+y+z=2, y:z=1:1, described preparation method comprises the following steps:
(1) compound concentration is manganese salt solution 10L, 0.01 ~ 0.5mol/L cobalt salt solution, 5 ~ 10L and 0.01 ~ 0.5mol/L chromium salt solution, the 5 ~ 10L of 0.02 ~ 2mol/L respectively, then by described three kinds of solution mixing, stirs 1h, obtains mixing salt solution;
(2) compound concentration is the precipitant solution of 1 ~ 5mol/L, and described precipitation reagent is one or more in NaOH, ammoniacal liquor and carbonic hydroammonium;
(3) 10L deionized water is added in a kettle. as end liquid, respectively described mixing salt solution and precipitant solution are slowly added in reactor by peristaltic pump, control reactant liquor pH=7 ~ 13, reaction temperature is room temperature, mixing speed 200 ~ 500rpm, until salting liquid is squeezed in reactor completely;
(4) according to the content of manganese in finished product manganate cathode material for lithium, take manganese dioxide in proportion, and added in the mixed liquor that step (3) obtains, continue stirring 1 ~ 2h, ageing 5 ~ 20h, then by solid-liquid product separately, with deionized water, gained presoma is washed to alkalescent;
(5) with Li:(Mn+Co+Cr) mol ratio be the ratio of 1:2, the presoma behind lithium source and described washing is joined in ball grinder, ball milling 2 ~ 5h, then 80 ~ 120 DEG C of oven dry, obtains persursor material;
(6) gained persursor material in step (5) is carried out double roasting respectively, bakes to burn the article is warming up to 500 ~ 850 DEG C with the heating rate of 4 DEG C/min, the insulation mode of 6 ~ 18 hours sinters, after baking sinters in the mode that the heating rate of 4 DEG C/min is warming up to 400 ~ 600 DEG C, be incubated 4 ~ 8h, sintering resulting materials is carried out fragmentation, screening, obtains described manganate cathode material for lithium.
Wherein said manganese salt is one or more in manganese chloride, manganese sulfate or manganese nitrate; Described cobalt salt is one or both in cobaltous sulfate or cobalt nitrate, and described chromic salts is one or more in chromium chloride, chromium sulfate or chromic nitrate.
Described lithium source be a kind of in lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide or wherein two or more with arbitrarily than mixture.Preferably, described lithium source is highly purified lithium carbonate.
Preferably, in step (5), the solvent carrying out employing during ball milling is deionized water.
The present invention in conjunction with liquid phase crystallization control legal system for presoma, be solvent again with deionized water, by liquid phase ball-milling method, each doped chemical is made to reach the mixing of atomic level, make the finished-product material structural integrity of burning till, reduce the dissolving of manganese in cell operations, prepared lithium manganate material capacity is high, and high temperature cyclic performance is excellent.In addition, this preparation method simply, safely, be easy to operation, be applicable to industrial production in enormous quantities.
Accompanying drawing explanation
Fig. 1 is that the manganate cathode material for lithium prepared of the present invention's five embodiments is at 55 DEG C of circulations cycle graph of 50 weeks.
Embodiment
Below in conjunction with embodiment, preparation method of the present invention is described in detail.
The molecular formula of the finished product manganate cathode material for lithium that the present invention obtains is LiMn
xco
ycr
zo
4,wherein x=1.88 ~ 1.96, x+y+z=2, y:z=1:1.
Embodiment 1
A preparation method for manganate cathode material for lithium, comprises the following steps:
1) prepare 2mol/L manganese sulfate solution 10L respectively, 0.1mol/L cobalt sulfate solution 10L, 0.05mol/L chromium sulfate solution 10L, by three kinds of solution mixing, stir 1h, obtain mixing salt solution;
2) compound concentration is respectively sodium hydroxide solution and each 10L of ammonia spirit of 1mol/L, is precipitated agent solution after mixing;
3) in 100L reactor, 10L deionized water is added as end liquid, the flow velocity of mixing salt solution and precipitant solution is controlled respectively with peristaltic pump, the two is squeezed in reactor simultaneously, controlling pH value of solution remains in 7 ~ 13 scopes, temperature of reaction kettle is room temperature, mixing speed is 200 turns/min, until salting liquid all adds in reactor;
4) by x=1.94 in finished product manganate cathode material for lithium molecular formula, take manganese dioxide in proportion and add in mixed liquor, after continuing to stir 1h, ageing 5h adopts solid-liquid separator by solid-liquid product separately, spends deionized water to alkalescent;
5) in Li:(Mn+Co+Cr) the ratio of mol ratio=1:2 lithium carbonate and presoma are added in ball grinder, ball milling 2h, takes out product and puts into baking oven, at 120 DEG C of dry 24h;
6) heated up with the heating rate of 4 DEG C/min by the persursor material obtained, carry out double roasting altogether, bakes to burn the article is at 700 DEG C of insulation 6h, and after baking, at 400 DEG C, is incubated 4 hours.Carry out fragmentation, screening afterwards, obtain manganate cathode material for lithium.
This positive electrode and lithium are assembled into button cell to electrode, and the first discharge specific capacity recording battery is 110.3mAh/g, and first charge-discharge cycle efficieny is 92.9%, 55 DEG C of circulations, 50 weeks rear capability retentions is 94.2%.
Embodiment 2
A preparation method for manganate cathode material for lithium, comprises the following steps:
1) prepare 0.2mol/L manganese sulfate solution 10L respectively, 0.02mol/L cobalt sulfate solution 10L, 0.02mol/L chromium nitrate solution 10L, by three kinds of solution mixing, stir 1h, obtain mixing salt solution;
2) compound concentration is respectively sodium hydroxide solution and each 10L of ammonia spirit of 2mol/L, is precipitated agent solution after mixing;
3) in 100L reactor, 10L deionized water is added as end liquid, the flow velocity of mixing salt solution and precipitant solution is controlled respectively with peristaltic pump, the two is squeezed in reactor simultaneously, controlling pH value of solution remains in 7 ~ 13 scopes, temperature of reaction kettle is room temperature, mixing speed is 300 turns/min, until salting liquid all adds in reactor;
4) by x=1.88 in finished product manganate cathode material for lithium molecular formula, take manganese dioxide in proportion and add in mixed liquor, ageing 8h after continuation stirring 1h, adopts solid-liquid separator by solid-liquid product separately, spends deionized water to alkalescent;
5) in Li:(Mn+Co+Cr) the ratio of mol ratio=1:2 a certain amount of lithium carbonate and presoma are added in ball grinder, ball milling 3h, takes out product and puts into baking oven 120 DEG C of dry 24h;
6) by step 5) in the precursor mixture that obtains carry out double roasting altogether with the heating rate of 4 DEG C/min, one burns 750 DEG C of insulation 10h, and two burn 500 DEG C of insulations 4 hours.Fragmentation, sieves and obtains required manganate cathode material for lithium.
This positive electrode and lithium are assembled into button cell to electrode, and the first discharge specific capacity recording battery is 114.4mAh/g, and first charge-discharge cycle efficieny is 94.3%, 55 DEG C of circulations, 50 weeks rear capability retentions is 94.1%.
Embodiment 3
A preparation method for manganate cathode material for lithium, comprises the following steps:
1) prepare 0.5mol/L manganese nitrate solution 10L respectively, 0.5mol/L cobalt nitrate solution 5L, 0.5mol/L chromium chloride solution 5L, by three kinds of solution mixing, stir 1h, obtain mixing salt solution;
2) compound concentration is respectively sodium hydroxide solution and each 10L of ammonia spirit of 3mol/L, is precipitated agent solution after mixing;
3) in 100L reactor, 10L deionized water is added as end liquid, the flow velocity of mixing salt solution and precipitant solution is controlled respectively with peristaltic pump, the two is squeezed in reactor simultaneously, controlling pH value of solution remains in 7 ~ 13 scopes, temperature of reaction kettle is room temperature, mixing speed is 300 turns/min, until salting liquid all adds in reactor.
4) by x=1.90 in finished product manganate cathode material for lithium molecular formula, take manganese dioxide in proportion and add in mixed liquor, ageing 12h after continuation stirring 2h, adopts solid-liquid separator by solid-liquid product separately, spends deionized water to alkalescent.
5) in Li:(Mn+Co+Cr) the ratio of mol ratio=1:2 a certain amount of lithium carbonate and presoma are added in ball grinder, ball milling 3h, takes out product and puts into baking oven 120 DEG C of dry 24h.
6) by step 5) in the precursor mixture that obtains carry out double roasting altogether with the heating rate of 4 DEG C/min, one burns 800 DEG C of insulation 12h, and two burn 500 DEG C of insulations 4 hours.Fragmentation, sieves and obtains required manganate cathode material for lithium.
This positive electrode and lithium are assembled into button cell to electrode, and the first discharge specific capacity recording battery is 112.3mAh/g, and first charge-discharge cycle efficieny is 95.0%, 55 DEG C of circulations, 50 weeks rear capability retentions is 95.3%.
Embodiment 4
A preparation method for manganate cathode material for lithium, comprises the following steps:
1) prepare 1mol/L manganese chloride solution 10L respectively, 0.3mol/L cobalt sulfate solution 5L, 0.3mol/L chromium chloride solution 5L, by three kinds of solution mixing, stir 1h, obtain mixing salt solution;
2) compound concentration is respectively sodium hydroxide solution and each 10L of ammonia spirit of 4mol/L, is precipitated agent solution after mixing;
3) in 100L reactor, 10L deionized water is added as end liquid, the flow velocity of mixing salt solution and precipitant solution is controlled respectively with peristaltic pump, the two is squeezed in reactor simultaneously, controlling pH value of solution remains in 7 ~ 13 scopes, temperature of reaction kettle is room temperature, mixing speed is 400 turns/min, until salting liquid all adds in reactor.
4) by x=1.92 in finished product manganate cathode material for lithium molecular formula, take manganese dioxide in proportion and add in mixed liquor, ageing 14h after continuation stirring 2h, adopts solid-liquid separator by solid-liquid product separately, spends deionized water to alkalescent.
5) in Li:(Mn+Co+Cr) the ratio of mol ratio=1:2 a certain amount of lithium carbonate and presoma are added in ball grinder, ball milling 4h, takes out product and puts into baking oven 120 DEG C of dry 24h.
6) by step 5) in the precursor mixture that obtains carry out double roasting altogether with the heating rate of 4 DEG C/min, one burns 850 DEG C of insulation 16h, and two burn 600 DEG C of insulations 6 hours.Fragmentation, sieves and obtains required manganate cathode material for lithium.
This positive electrode and lithium are assembled into button cell to electrode, and the first discharge specific capacity recording battery is 116.2mAh/g, and first charge-discharge cycle efficieny is 96.1%, 55 DEG C of circulations, 50 weeks rear capability retentions is 98.2%.
Embodiment 5
A preparation method for manganate cathode material for lithium, comprises the following steps:
1) prepare 0.02mol/L manganese chloride solution 10L respectively, 0.01mol/L cobalt nitrate solution 10L, 0.01mol/L chromium chloride solution 10L, by three kinds of solution mixing, stir 1h, obtain mixing salt solution;
2) compound concentration is respectively sodium hydroxide solution and each 10L of ammonia spirit of 5mol/L, is precipitated agent solution after mixing;
3) in 100L reactor, 10L deionized water is added as end liquid, mixing salt solution and precipitant solution flow velocity is controlled respectively with peristaltic pump, the two is squeezed in reactor simultaneously, controlling pH value of solution remains in 7 ~ 13 scopes, temperature of reaction kettle is room temperature, mixing speed is 500 turns/min, until salting liquid all adds in reactor.
4) by x=1.96 in finished product manganate cathode material for lithium molecular formula, take manganese dioxide in proportion and add in mixed liquor, ageing 20h after continuation stirring 2h, adopts solid-liquid separator by solid-liquid product separately, spends deionized water to alkalescent.
5) in Li:(Mn+Co+Cr) the ratio of mol ratio=1:2 a certain amount of lithium carbonate and presoma are added in ball grinder, ball milling 5h, takes out product and puts into baking oven 120 DEG C of dry 24h.
6) by step 5) in the precursor mixture that obtains carry out double roasting altogether with the heating rate of 4 DEG C/min, one burns 900 DEG C of insulation 18h, and two burn 600 DEG C of insulations 8 hours.Fragmentation, sieves and obtains required manganate cathode material for lithium.
This positive electrode and lithium are assembled into button cell to electrode, and the first discharge specific capacity recording battery is 114.9mAh/g, and first charge-discharge cycle efficieny is 96.0%, 55 DEG C of circulations, 50 weeks rear capability retentions is 96.5%.
Lithium manganate material uniform composition prepared by the present invention, Stability Analysis of Structures, resulting materials chemical property is good, and specific capacity is high, and high temperature cyclic performance is excellent.This kind of method technique is simple, is easy to operation, is applicable to large-scale production in enormous quantities.
Claims (5)
1. a preparation method for manganate cathode material for lithium, the molecular formula of described manganate cathode material for lithium is LiMn
xco
ycr
zo
4, wherein x=1.88 ~ 1.96, x+y+z=2, y:z=1:1, is characterized in that comprising the following steps:
(1) compound concentration is manganese salt solution 10L, 0.01 ~ 0.5mol/L cobalt salt solution, 5 ~ 10L and 0.01 ~ 0.5mol/L chromium salt solution, the 5 ~ 10L of 0.02 ~ 2mol/L respectively, then by described three kinds of solution mixing, stirs 1h, obtains mixing salt solution;
(2) compound concentration is the precipitant solution of 1 ~ 5mol/L, and described precipitation reagent is one or more in NaOH, ammoniacal liquor and carbonic hydroammonium;
(3) 10L deionized water is added in a kettle. as end liquid, respectively described mixing salt solution and precipitant solution are slowly added in reactor by peristaltic pump, control reactant liquor pH=7 ~ 13, reaction temperature is room temperature, mixing speed 200 ~ 500rpm, until salting liquid is squeezed in reactor completely;
(4) according to the content of manganese in finished product manganate cathode material for lithium, take manganese dioxide in proportion, and added in the mixed liquor that step (3) obtains, continue stirring 1 ~ 2h, ageing 5 ~ 20h, then by solid-liquid product separately, with deionized water, gained presoma is washed to alkalescent;
(5) with Li:(Mn+Co+Cr) mol ratio be the ratio of 1:2, the presoma behind lithium source and described washing is joined in ball grinder, ball milling 2 ~ 5h, then 80 ~ 120 DEG C of oven dry, obtains persursor material;
(6) gained persursor material in step (5) is carried out double roasting respectively, bakes to burn the article is warming up to 500 ~ 850 DEG C with the heating rate of 4 DEG C/min, the insulation mode of 6 ~ 18 hours sinters, after baking sinters in the mode that the heating rate of 4 DEG C/min is warming up to 400 ~ 600 DEG C, be incubated 4 ~ 8h, sintering resulting materials is carried out fragmentation, screening, obtains described manganate cathode material for lithium.
2. preparation method according to claim 1, is characterized in that: manganese salt used is one or more in manganese chloride, manganese sulfate or manganese nitrate; Described cobalt salt is one or both in cobaltous sulfate or cobalt nitrate, and described chromic salts is one or more in chromium chloride, chromium sulfate or chromic nitrate.
3. preparation method according to claim 1, is characterized in that: lithium source used be a kind of in lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide or wherein two or more with arbitrarily than mixture.
4. preparation method according to claim 1, is characterized in that: described lithium source is highly purified lithium carbonate.
5. preparation method according to claim 1, it is characterized in that: in step (5), the solvent carrying out employing during ball milling is deionized water.
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| CN1562771A (en) * | 2004-04-07 | 2005-01-12 | 中信国安盟固利电源技术有限公司 | Spherical shaped lithium manganate and preparation method |
| CN102903902A (en) * | 2012-09-27 | 2013-01-30 | 多氟多化工股份有限公司 | Doping type spinel lithium manganate electrode material and preparation method thereof |
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| CN1562771A (en) * | 2004-04-07 | 2005-01-12 | 中信国安盟固利电源技术有限公司 | Spherical shaped lithium manganate and preparation method |
| CN102903902A (en) * | 2012-09-27 | 2013-01-30 | 多氟多化工股份有限公司 | Doping type spinel lithium manganate electrode material and preparation method thereof |
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