CN1485278A - Preparation method for secondary crystal lithium cobalt acid of positive electrode material of lithium ion cell - Google Patents
Preparation method for secondary crystal lithium cobalt acid of positive electrode material of lithium ion cell Download PDFInfo
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- CN1485278A CN1485278A CNA021313121A CN02131312A CN1485278A CN 1485278 A CN1485278 A CN 1485278A CN A021313121 A CNA021313121 A CN A021313121A CN 02131312 A CN02131312 A CN 02131312A CN 1485278 A CN1485278 A CN 1485278A
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Abstract
A method of preparing new-style lithium cobaltic acid with the second-pellet configuration, comprises the method of preparing the raw material of the second-pellet cobalt hydroxide and Co3O4 and the baking technology. Prepared second-pellet lithium cobaltic acid has a high specific volume, excellent heavy-current discharge, a long cycle life, which is the best material for positive electrode of mobilephones. Taking a compound of NH4+ as the complexing agent, sodium hydroxide as the precipitating agent, controlling parameters, cobalt hydroxide with a special configuration is prepared. The product has a uniform particle size which is controllable, has a configuration of approximating pellets. The packing density is 1.5-2.0g/cm3, the specific surface area is 5-25m2/g. Prepared Co3O4 with a second-pellet configuration (see figure 1) has a good dispersion property, the median particle size is 2-10mum, the packing density is 1.5-2.0g/cm3, the specific surface area is 10-50m2/g.
Description
The invention relates to the preparation method of novel secondary crystal lithium cobalt acid, it comprises the cobaltous hydroxide, tricobalt tetroxide of novel secondary spherical structure and producing of cobalt acid lithium.
Lithium ion battery is because of it has the voltage height, capacity is big, self-discharge rate is little, memory-less effect, do not contain characteristics such as Toxic matter, use temperature scope is wide, shown good prospects for application in fields such as portable electric appts, electromobile, space technology, national defense industry, since nineteen ninety Japan Sony Corporation takes the lead in succeeding in developing and realizes commercialization, the exploitation that is subjected to extensive concern in recent years and the focus of achievements conversion have been become.With Japan is example: lithium ion battery annual growth has in recent years accounted for 20% in secondary cell, and its rate of utilization accounted for 95% in 2000 according to measuring and calculating in notebook computer, and mobile telephone accounts for more than 50%.China is since reform and opening-up, and household electrical appliance and electronics enter family in a large number, develop very rapid.Calendar year 2001, the whole nation had 100,012,000 of mobile telephones, and its rate of increase occupies first place in the world.The demand of notebook computer, camera, electromobile is also also enlarging accordingly in demand growing, high tension battery, lithium ion battery has vast market prospect equally in China, the foreseeable future, lithium ion battery will become 21 century power truck (EV) and hybrid electric vehicle (HEV) one of the most competitive power.Though China is a semiconductor production and big trading nation, also be battery production first big country in the world, only battery production in 1997 is about 12,000,000,000, accounts for 1/3rd of world wide production, but the product majority is low grade products such as pasty state battery, cell with paperboard partition, has produced alkaline cell in recent years.At the initial stage eighties, beginning one's study is used for the button cell that electronic calculator uses, and introduced lithium metal battery from the U.S. and use for defence and military the nineties, the development work of having carried out lithium ion battery at home simultaneously.With market survey with market consultation and the market forecast that celebrated U.S. Cahners In-Stat Group delivers relevant mobile phone in June 14 calendar year 2001.The mobile phone sales volume of prediction expression world market in 2003 will reach 1,000,000,000 ones, be 400,000,000 ones in U.S.'s mobile phone sales volume in 2000 only, and this numeral in 1999 only be 2.77 hundred million ones.
The positive and negative electrode of lithium ion battery is to adopt to supply lithium ion freely to embed the active material of deviating from, and during charging, lithium ion is overflowed from positive pole and embedded negative pole, then deviates from from negative pole during discharge, embeds anodal.With cobalt acid lithium is positive electrode material, and graphite is that the lithium ion battery of negative material is an example, and it discharges and recharges reaction formula and is:
Lithium intercalation compound as positive electrode material is the depots of lithium ion, generally speaking, it should satisfy following some:
(1) in the discharge voltage range that requires, has the electrochemistry consistency with electrolyte solution;
(2) Wen He kinetics of electrode process;
(3) high reversibility;
(4) under the full lithiumation state, property stable in the air is good.
The active substance of the positive electrode material that can use as commercialization mainly is a cobalt acid lithium at present, though there are a plurality of units in China at development and production cobalt acid lithium, but it is reported that product is the traditional cobalt acid lithium with a spherical structure, the major defect of this product is: when heavy-current discharge, loading capacity is little, life-span is short, can't satisfy the requirement of producing the high performance lithium ion battery that mobile telephone uses.In order to overcome this defective, we are from the used raw material of preparation high-performance cobalt acid lithium, the microtexture of its initial feed and size are improved and innovated, by reasonably design and optimal preparation technology and parameter, successfully develop high-performance cobalt acid lithium of new generation with special secondary spherical structure.This secondary crystal lithium cobalt acid material is the regeneration product of existing traditional cobalt acid lithium, performances such as the specific surface area of its product, heavy-current discharge capacity, cycle life all improve to some extent, and do not need additionally to increase cost, outstanding especially is the obvious raising of " discharge-rate ".Discharge-rate is very important performance index of battery, it is meant that battery emits big capacity when heavy-current discharge, this exactly is fit to the requirement of mobile telephone, because during mobile telephone work is to discharge with pulse mode, pulsed current is very big, adopt lithium ion battery capacity when this heavy-current discharge of existing traditional cobalt acid lithium obviously to descend at present, thereby shortened battery life.In addition, compare with existing traditional cobalt acid lithium, the overcharge safety of secondary crystal lithium cobalt acid is good, thereby is particularly suitable for the mobile telephone lithium ion battery.
The present invention is on the basis of existing traditional cobalt acid lithium research, adopt the liquid phase synthetic system and the synthetic technology of unique exploitation, a kind of cobaltous hydroxide with nearly spheroidal aggravation pattern is provided, and then be sintered into secondary ball tricobalt tetroxide, adopt special high temperature solid-state synthesis technique to prepare novel secondary crystal lithium cobalt acid as raw material again.This cobalt acid lithium be by primary particle size be small-particle about 0.5 μ m-3 μ m to be agglomerated into aggregate particle size be the granuloplastic of the nearly spheroid of 5-15 μ m, have typical α-NaFeO
2Layered crystal structure.The perfection of this type material crystalline structure, chemical property are good, stable performance, preparation technology are simple, are mobile telephones with lithium ion battery ideal positive electrode material.
For achieving the above object, the technical measures that this patent adopted are:
1) in liquid phase synthesis process, reasonably selected the cobalt precipitation system, on request cobalt metal is dissolved into the certain density aqueous solution, in this solution, add complexing agent, precipitation agent then, make the cobalt precipitation in the solution.Throw out makes the cobaltous hydroxide of nearly conglobulation body structure after making beating, washing, filtration, drying, make after calcining as the synthetic raw materials used tricobalt tetroxide with special construction of secondary crystal lithium cobalt acid then.
2) in the high temperature solid-state synthesis technique, adopting the tricobalt tetroxide with special two secondary spherical structures and the lithium salts (as lithium hydroxide, lithium nitrate or Quilonum Retard) of the present invention's preparation is raw material, according to certain stoichiometry thorough mixing, through the granulation engineering, in the long-time roasting of cold zone, the lithium salts fusion is also fully soaked in the lattice of tricobalt tetroxide, form uniform lamellar phase nucleus and control nucleus formation, and then nucleus and particle are grown up through high-temperature calcination.By regulating temperature, time, atmosphere and the roasting mode of roasting, can change size and the specific surface area and the density of primary particle and second particle according to demand.Make the secondary crystal lithium cobalt acid material that lithium ion battery is used by operations such as pulverizing, classifications at last.
The production method of tricobalt tetroxide generally is to add the hydrate that the sodium hydroxide neutralizing hydrolysis obtains cobalt/cobalt oxide in cobalt nitrate solution, calcines under comparatively high temps then and obtains cobalt oxide.The cobalt oxide conglomeration of producing like this is too hard, and actual grain size is also very thick, can't obtain the spheric product.
The production method of general industry tricobalt tetroxide is to produce cobalt oxalate with oxalate precipitation method, the cobalt oxide that obtains through thermolysis is a needle-like again, and its brilliant degree is thick, and granularity generally also is about 10 μ m, be difficult to its median size is controlled at 2-4 μ m, also can't obtain the spheric product.
PREPARATION OF COBALT OXIDE FOR has been made extensive work abroad, the mean particle size of the cobalt oxide that uses now as Siemens Company is 10 μ m, the equal 9-16 μ of the median size m of the cobalt oxide that Sweden ABB AB uses now.The average diameter that is used for electronic ceramics cobalt oxide already that has only certain company of France to produce at present can reach 3.5 μ m, and these products all will pass through superfine grinding, can use, but still can not form the spheric cobalt oxide.
Though adopt the ultra-fine spherical cobaltous carbonate of the sedimentary liquid phase building-up process energy output of amine carbonate or Ammonium bicarbonate food grade, can obtain subglobose cobalt oxide after the calcining.But the median size of products obtained therefrom can not be used to produce the high-performance cobalt acid lithium with secondary spherical structure that lithium ion battery is used at the 0.2-0.6 mu m range owing to too carefully and not have the reunion characteristic.
Method of the present invention is to adopt to contain NH
4 +The ionic compound is a precipitation agent as complexing agent, sodium hydroxide, by strict control process parameters, successfully synthesizes the cobaltous hydroxide with special construction, the gained sample granularity is even, and globule size is controlled, good fluidity, nearly ball-type (see figure 1), tap density is 1.5-2.0g/cm
3, specific surface area is 5-25m
2/ g, its structure is the agglomerating particles that many molecules are formed.Make the tricobalt tetroxide that meets the requirements after the calcining.Product has secondary spherical structure (see figure 2), favorable dispersity, meso-position radius 2-10 μ m, and tap density is 1.5-2.0g/cm
3, specific surface area is 10-50m
2/ g.Novel process of this preparation secondary spherical structure tricobalt tetroxide has originality, for the deep processing and the preparation secondary ball high-performance cobalt acid lithium of cobalt finds a new approach, and will create good economic benefit.
The feature of present method is as follows:
1. in cobalt salt solution, add a certain amount of NH that contains
4 +Ionic compound and precipitation agent.Temperature of reaction is at 30-90 ℃; 1 mole metal cobalt, NH
4 +The add-on of ionic compound is the 2-8 mole, NH
4 +The effect of ionic compound is and the cobalt complexing formation speed and the shape of control cobaltous hydroxide.
2.NaOH concentration be 15-50%, its feed rate and cobalt mol ratio are 1-5.
3. the pH of control precipitin reaction is 8.0-12.0.
4. producing of tricobalt tetroxide is that above-mentioned cobaltous hydroxide with after a certain amount of oven dry is put in the stove, in the cooling naturally after 5-15 hour of 300-700 ℃ of temperature constant temperature, takes out, and is tricobalt tetroxide.
This tricobalt tetroxide by the mol ratio of lithium/cobalt be 0.97～1.15 with the lithium salts thorough mixing, through granulation, in 600～1000 ℃ of segmentation roastings of temperature, temperature rise rate is 1～10 ℃/min, roasting time 5h～50h.
Embodiment 1
In the reactor of the cobalt nitrate solution that contains cobalt concentration 120g/l, press NH
3/ Co=4: 1 adding contains NH
4 +The ionic compound slowly adds 30% NaOH solution, and temperature of reaction was reacted 24 hours under 60 ℃.Filter, wash, dry, promptly get cobaltous hydroxide.Its sem photograph is seen Fig. 3, records tap density 1.65g/cm
3, specific surface area is 15.9m
2/ g, middle particle diameter D
50=4.68 μ m.This cobaltous hydroxide fuses 10hr under 500 ℃, get tricobalt tetroxide, and its sem photograph is seen Fig. 4, tap density 1.60g/cm
3, specific surface area is 38.1m
2/ g, middle particle diameter D
50=4.75 μ m.After getting this tricobalt tetroxide 18.50g and the granulation of 9.04g Quilonum Retard thorough mixing, fuse 10hr under 850 ℃, can get cobalt acid lithium 22.28g.Its Electronic Speculum figure sees Fig. 5, records tap density 2.30g/cm
3, specific surface area is 0.67m
2/ g, middle particle diameter D
50=7.25 μ m.
Gained cobalt acid lithium is dressed up simulated battery, and the simulated battery septation is the celgard2300 type, and negative pole is a metal lithium sheet.Recording its initial specific storage is 155mAh/g, after 20 circulations, and capacity attenuation 1.68%.Discharge-rate curve such as Figure 12.
Embodiment 2
Difference from Example 1, the concentration of Co are 60g/L.Cobaltous hydroxide Electronic Speculum figure sees Fig. 6, gets the tap density 1.61g/cm of cobaltous hydroxide
3, specific surface area is 12.5m
2/ g, middle particle diameter 4.29 μ m.Get this cobaltous hydroxide 34.24g, fuse 10hr under 500 ℃, can get cobalt oxide 31.91g, its Electronic Speculum figure is following to be seen and records tap density 1.64g/cm by Fig. 7
3, specific surface area is 29.4m
2/ g, middle particle diameter 5.27 μ m.Get this cobalt oxide 18.50g, behind 9.04g Quilonum Retard thorough mixing, fuse 10hr under 850 ℃, can get cobalt acid lithium 22.24g.Its Electronic Speculum figure is following to be seen and records tap density 2.31g/cm by Fig. 8
3, specific surface area is 0.60m
2/ g, middle particle diameter D
50=7.39 μ m.
Gained cobalt acid lithium is dressed up simulated battery, and the simulated battery septation is the celgard2300 type, and negative pole is a metal lithium sheet.Recording its initial specific storage is 154mAh/g, 20 circulation back specific storage decay 1.58%.
Embodiment 3
Contain NH with the difference of embodiment 2 for not adding
4 +The ionic compound.The Electronic Speculum of the cobaltous hydroxide of gained is Fig. 9, with the difference of Fig. 3 be granularity superfine, do not reunite.Record tap density 1.23g/cm
3, specific surface area is 24.0m
2/ g,, middle particle diameter 0.81 μ m.The Electronic Speculum figure of the cobalt oxide of gained is Figure 10 after the roasting, with the difference of Fig. 4 be that granularity is little, do not reunite.Record tap density 1.25g/cm
3, specific surface area is 47.0m
2/ g, middle particle diameter 0.67 μ m.These data and preceding two embodiment have obvious difference.The Electronic Speculum of the cobalt acid lithium that makes with this cobalt oxide is seen Figure 11, records tap density 1.55g/cm
3, specific surface area is 1.86m
2/ g, meso-position radius 4.62 μ m.
Gained cobalt acid lithium is dressed up simulated battery, and the simulated battery septation is the celgard2300 type, and negative pole is a metal lithium sheet.Recording its initial specific storage is 141mAh/g, after 20 circulations, and specific storage decay 2.80%.
Embodiment 1 and the result of embodiment 2 show: when the concentration of Co was 60g/l and 120g/l, quality product was identical; Compare with embodiment 3, contain NH
4 +The effect of ionic compound is that significantly it makes cobaltous hydroxide and cobalt oxide be spherical, and the surface has molecule.
Novel cobalt acid lithium specific storage with secondary spherical structure is big, and it is little to decay, and particularly when heavy-current discharge, the decay of capacity is slower than other product, the discharge-rate height.
Claims (10)
1. the preparation method of a mobile telephone usefulness high performance lithium ion battery anode material secondary crystal lithium cobalt acid wherein makes secondary crystal lithium cobalt acid by roasting with the raw material that contains lithium with cobaltous hydroxide or tricobalt tetroxide with secondary spherical structure after mixing.
2. according to the method for claim 1, in cobalt salt solution, add a certain amount of NH that contains
4 +Ionic compound and precipitation agent stir and precipitin reaction, produce needed secondary ball cobaltous hydroxide powder material.
3. according to the method for claim 1, the tricobalt tetroxide of secondary spherical structure is formed by the cobaltous hydroxide calcining of secondary spherical structure.
4. according to the method for claim 2, temperature of reaction is at 30-90 ℃; 1 mole metal cobalt contains NH
4 +Ionic compound add-on is the 2-8 mole, contains NH
4 +The effect of ionic compound is and the cobalt ion complexing formation speed and the shape of control cobaltous hydroxide.Precipitation agent can generate cobaltous hydroxide with the NaOH reaction.The concentration of NaOH is 15-50%, and its feed rate and cobalt mol ratio are 1-5.The pH of control precipitin reaction is 8.0-12.0.
5. according to the method for claim 3, secondary ball cobaltous hydroxide is sintered into the temperature of secondary ball tricobalt tetroxide at 300-700 ℃, and calcination time is 5-15 hour.
6. according to the method for claim 1, selected cobalt raw material comprises that selected lithium raw material is LiOHH according to the cobaltous hydroxide with secondary spherical structure or the tricobalt tetroxide of the method preparation of aforesaid right requirement 3-6
2O, LiNO3 or Li
2CO
3Wherein the mol ratio of lithium/cobalt is 0.97～1.15.Cobalt raw material and lithium raw material add binding agent and granulation when mixing.
7. according to the method for claim 1, maturing temperature is 600～1000 ℃, and temperature rise rate is 1～10 ℃/min, roasting time 5h～50h.Prepared secondary crystal lithium cobalt acid has typical α-NaFeO
2The stratiform crystal phase structure, and have the apparent pattern of unique secondary ball aggressiveness.
8. according to the description of claim 2, the specific surface area of secondary ball cobaltous hydroxide is 5-25m
2/ g, the tap density of secondary ball cobaltous hydroxide is 1.5-2.0g/cm
3
9. according to the description of claim 3, the specific surface area of secondary ball tricobalt tetroxide is 10-50m
2/ g, the tap density of secondary ball tricobalt tetroxide is 1.5-2.0g/cm
3
10. according to the description of claim 1, a median size of secondary crystal lithium cobalt acid is 0.5～3 μ m, quadratic average particle diameter 5～15 μ m.The specific surface area of secondary crystal lithium cobalt acid is 0.2-0.8g/cm
3The tap density of secondary crystal lithium cobalt acid is 2.0-2.6m
2/ g.Prepared secondary crystal lithium cobalt acid has 4.3～3.0V continuous discharge voltage characteristic with respect to metal Li, and specific discharge capacity surpasses 140mAh/g, and average every circulation primary capacity attenuation rate is less than 0.05～0.1%.Prepared secondary crystal lithium cobalt acid is under the 1.5C multiplying power discharging, and capability retention is more than 95%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319192C (en) * | 2005-05-31 | 2007-05-30 | 中国科学院广州化学研究所 | Method for processing positive pole material of lithium cobalt acid in lithium ion battery |
| CN1322614C (en) * | 2005-07-08 | 2007-06-20 | 清华大学 | Macro-grain LiCoO2 of anode material for lithium ion cell and preparing process thereof |
| CN100420072C (en) * | 2004-06-29 | 2008-09-17 | 太阳集团高科技发展有限责任公司 | Method for preparing active lithium cobalt oxide |
| CN101694874B (en) * | 2009-10-21 | 2012-01-11 | 南通瑞翔新材料有限公司 | Process for preparing lithium cobalt oxide of lithium-ion secondary battery cathode materials |
| CN103435108A (en) * | 2013-08-26 | 2013-12-11 | 无锡中经金属粉末有限公司 | Process for synthesizing large-granular spherical lithium cobalt oxide with high tap density |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105384197A (en) * | 2014-09-05 | 2016-03-09 | 河南科隆新能源有限公司 | Spherical cobalt hydroxide and preparation method thereof |
| CN105845927A (en) * | 2016-03-25 | 2016-08-10 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery cathode material lithium cobalt oxide |
| CN106486665A (en) * | 2016-11-01 | 2017-03-08 | 北大先行科技产业有限公司 | A kind of low internal resistance lithium cobaltate cathode material and its preparation method and application |
| CN106587170A (en) * | 2016-11-30 | 2017-04-26 | 兰州金川新材料科技股份有限公司 | Preparation method of cobaltosic oxide with rare earth element doped body phase |
| US10351440B2 (en) * | 2011-05-31 | 2019-07-16 | Freeport Colbalt Oy | Lithium cobalt oxide material |
-
2002
- 2002-09-27 CN CNB021313121A patent/CN100488882C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420072C (en) * | 2004-06-29 | 2008-09-17 | 太阳集团高科技发展有限责任公司 | Method for preparing active lithium cobalt oxide |
| CN1319192C (en) * | 2005-05-31 | 2007-05-30 | 中国科学院广州化学研究所 | Method for processing positive pole material of lithium cobalt acid in lithium ion battery |
| CN1322614C (en) * | 2005-07-08 | 2007-06-20 | 清华大学 | Macro-grain LiCoO2 of anode material for lithium ion cell and preparing process thereof |
| CN101694874B (en) * | 2009-10-21 | 2012-01-11 | 南通瑞翔新材料有限公司 | Process for preparing lithium cobalt oxide of lithium-ion secondary battery cathode materials |
| US10351440B2 (en) * | 2011-05-31 | 2019-07-16 | Freeport Colbalt Oy | Lithium cobalt oxide material |
| CN103435108A (en) * | 2013-08-26 | 2013-12-11 | 无锡中经金属粉末有限公司 | Process for synthesizing large-granular spherical lithium cobalt oxide with high tap density |
| CN105384197A (en) * | 2014-09-05 | 2016-03-09 | 河南科隆新能源有限公司 | Spherical cobalt hydroxide and preparation method thereof |
| CN105384197B (en) * | 2014-09-05 | 2018-10-19 | 河南科隆新能源有限公司 | spherical cobalt hydroxide and preparation method thereof |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105845927A (en) * | 2016-03-25 | 2016-08-10 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery cathode material lithium cobalt oxide |
| CN106486665A (en) * | 2016-11-01 | 2017-03-08 | 北大先行科技产业有限公司 | A kind of low internal resistance lithium cobaltate cathode material and its preparation method and application |
| CN106587170A (en) * | 2016-11-30 | 2017-04-26 | 兰州金川新材料科技股份有限公司 | Preparation method of cobaltosic oxide with rare earth element doped body phase |
| CN106587170B (en) * | 2016-11-30 | 2018-05-15 | 兰州金川新材料科技股份有限公司 | A kind of cobaltosic oxide preparation method of bulk phase-doped rare earth element |
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