CN103435108B - Process for synthesizing large-granular spherical lithium cobalt oxide with high tap density - Google Patents
Process for synthesizing large-granular spherical lithium cobalt oxide with high tap density Download PDFInfo
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- CN103435108B CN103435108B CN201310377003.2A CN201310377003A CN103435108B CN 103435108 B CN103435108 B CN 103435108B CN 201310377003 A CN201310377003 A CN 201310377003A CN 103435108 B CN103435108 B CN 103435108B
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Abstract
The invention relates to a process for synthesizing large-granular spherical lithium cobalt oxide with high tap density, which belongs to the technical field of secondary batteries. The large-granular spherical lithium cobalt oxide with high tap density is prepared by the following steps: solution matching, mixed alkali liquor matching, synthesizing, drying, calcining, mixing and secondary calcining. Compared with the prior art, the process provided by the invention can be applied to the production of lithium batteries and the existing small-granular lithium cobalt oxide with low bulk density and low tap density in anode materials can be completely replaced, thereby not only being capable of lowering the production cost and improving the stability of product quality, but also having advantages in such aspects as life cycle, low temperature discharge, high voltage, and the like, and as a result, a new revolution for improving the production process of lithium batteries and power batteries of the nation can be brought.
Description
Technical field
The present invention relates to a kind of bulky grain high-tap density spherical lithium cobalt synthesis technique synthesis technique, be specifically related to a kind of capacity, efficiency and life-span to secondary cell to play the spherical lithium cobalt synthesis technique of key effect, belong to secondary battery technology.
Background technology
Along with the development of China's economy, science and technology, the use of the energy is also increased thereupon, especially developing rapidly of industry, larger to the consumption of battery power, the hazardous substance of generation easily causes the destruction of biological environment.Therefore, country proposes higher requirement to the use of the energy, not only requires to improve the service efficiency of the energy, and will reach energy-saving and emission-reduction, strengthens the order ground of natural, ecological protection.Therefore, improve battery power device structure, particularly the preparation of high purity battery energy and material is very important.
Cobalt acid lithium, LiMn2O4, LiFePO4, etc. be the positive electrode of manufacturing at present several keys of lithium ion chargeable battery.Recently research is thought: cobalt acid lithium, LiMn2O4, LiFePO4 are a kind of cell positive materials of excellent performance.It can significantly improve the performance of battery, improve specific capacity and the high-output power of battery, improve the charge and discharge circulation life of battery, improve overcharging resisting power and reduce self-discharge phenomenon etc., make storage battery develop into possibility to high energy, small-sized, light weight, safety, the aspect such as pollution-free.
At present, all ubiquity particle is little for most of cobalt acid lithiums, tap density is little, granularity is inhomogeneous, after needing high-temperature calcination, production process pulverizes the process of carrying out again classification, to the crystalline structure destructible of cobalt acid lithium, thereby affect it at capacity and the high-output power made after lithium battery, the giving full play to of charge and discharge circulation life efficiency and life-span.
Summary of the invention
The object of the invention is to overcome existing weak point, a kind of bulky grain high-tap density spherical lithium cobalt synthesis technique is provided; After calcining, without pulverizing and classification, directly vibrating screen sieves, and produces bulky grain, good uniformity, and tap density is large, good stability spherical lithium cobalt cobalt.
According to technical scheme provided by the invention, a kind of bulky grain high-tap density spherical lithium cobalt synthesis technique, concrete steps are as follows:
(1) solution ratio: get the cobalt salt solution that mass concentration is 1-1.5mol/L, be diluted to 0.2-0.5mol/L with deionized water; Getting sodium carbonate deionized water, to be made into the sodium carbonate liquor of 2-2.5mol/L concentration for subsequent use;
(2) mixed alkali liquor proportioning: the sodium carbonate liquor of getting by volume step (1) configuration: ammoniacal liquor: the ratio of carbonic hydroammonium 115-125:1-1.5:0.8-1.2 is mixed, and obtains mixed alkali liquor; Described ammoniacal liquor mass concentration is 2 ~ 2.5mol/L, and carbonic hydroammonium mass concentration is 2-2.5mol/L;
(3) synthetic: take and flow mode and reactor adds pipe reaction, and continuous pulp discharge;
Concrete steps for: the mixed alkali liquor of getting cobalt salt solution that step (1) configures and step (2) configuration with and the mode of stream before pump, add in reactor; Control step a mixed solution pH value between 7.5-7.8; Keep synthesis temperature at 80-85 DEG C; Control residence time of material at 4-12h, mixing speed is 90-120r/min; Circulating pump rotating speed 2400-3200r/min; After finishing, reaction obtains gained spherical cobaltous carbonate; Gained spherical cobaltous carbonate keeps 80-85 DEG C of precipitation 1-2h;
(4) dry: the deionized water of getting 90-95 DEG C of gained reactant spherical cobaltous carbonate in centrifuge, clean to pH be neutrality, centrifuge speed is 2500-3500r/min, 90-120 DEG C of oven dry;
(5) calcining: the spherical cobaltous carbonate after drying, at 850-950 DEG C of calcining 8-12h, is obtained to cobaltosic oxide;
(6) mix: after the cobaltosic oxide after calcining is directly sieved, then it is mixed according to weight ratio 1.5-1.7:1-1.2 with lithium carbonate or lithium hydroxide;
(7) secondary clacining: the material after mixing, at 900-950 DEG C of temperature lower calcination 8-12h, is then sieved and can obtain bulky grain high-tap density spherical lithium cobalt.
Described cobalt salt solution is cobalt chloride, cobaltous sulfate or cobalt nitrate solution.
In described step (6), (7), crossing grit number is 200-250 order.
Beneficial effect of the present invention: the bulky grain high-tap density spherical lithium cobalt that the present invention produces has uniform particles (granularity D
50at 20 ~ 50 microns), good fluidity, the advantage such as good stability tap density is large, and apparent density is large, its LiCo2 feature embodies completely on XRD, capacity, efficiency and life-span to lithium battery play key effect.Compared with prior art: the general synthetic raising reactor mixing speed that adopts improves the complete of sphericity now, but power requirement can only reach very greatly and also 300 ~ 500r/min; And patent of the present invention is to add pipe reaction to increase circulating pump rotating speed 2400 ~ 3200r/min under the prerequisite of normal reaction still mixing speed 90 ~ 120r/min again, and control the time of staying of material at reactor, complexing with ammonium, so improve sphericity and packing greatly, made it AD, TD improves greatly.The stability of product quality like this, and at cycle life, low temperature discharge, the aspects such as high voltage have more advantage, with the dynamic lithium battery that is suitable for large current density.
Brief description of the drawings
Bulky grain high-tap density spherical lithium cobalt SME figure prepared by Fig. 1 embodiment 1.
Bulky grain high-tap density spherical lithium cobalt XRD figure prepared by Fig. 2 embodiment 1.
Bulky grain high-tap density spherical lithium cobalt particle size distribution figure prepared by Fig. 3 embodiment 1.
Embodiment
Embodiment 1
A kind of bulky grain high-tap density spherical lithium cobalt synthesis technique, concrete steps are as follows:
(1) solution ratio: get the cobalt salt solution that mass concentration is 1mol/L, be diluted to 0.2mol/L with deionized water; Getting sodium carbonate deionized water, to be made into the sodium carbonate liquor of 2mol/L concentration for subsequent use;
(2) mixed alkali liquor proportioning: the sodium carbonate liquor of getting by volume step (1) configuration: ammoniacal liquor: the ratio of carbonic hydroammonium 115:1:0.8 is mixed, and obtains mixed alkali liquor; Described ammoniacal liquor mass concentration is 2mol/L, and carbonic hydroammonium mass concentration is 2mol/L;
(3) synthetic: take and flow mode and reactor adds pipe reaction, and continuous pulp discharge;
Concrete steps for: the mixed alkali liquor of getting cobalt salt solution that step (1) configures and step (2) configuration with and the mode of stream before pump, add in reactor; Control step a mixed solution pH value between 7.5; Keep synthesis temperature at 80 DEG C; Control residence time of material at 4h, mixing speed is 90r/min; Circulating pump rotating speed 2400r/min; After finishing, reaction obtains gained spherical cobaltous carbonate; Gained spherical cobaltous carbonate keeps 80-85 DEG C of precipitation 1h;
(4) dry: get the gained reactant spherical cobaltous carbonate deionized water of 90 DEG C in centrifuge, clean to pH be neutrality, centrifuge speed is 2500r/min, 90 DEG C of oven dry;
(5) calcining: the spherical cobaltous carbonate after drying, at 850 DEG C of calcining 8h, is obtained to cobaltosic oxide;
(6) mix: after the cobaltosic oxide after calcining is directly sieved, then it is mixed according to weight ratio 1.5:1 with lithium carbonate or lithium hydroxide;
(7) secondary clacining: the material after mixing, at 900 DEG C of temperature lower calcination 8h, is then sieved and can obtain bulky grain high-tap density spherical lithium cobalt.
Described cobalt salt solution is cobalt chloride, cobaltous sulfate or cobalt nitrate solution.
In described step (6), (7), crossing grit number is 250 orders.
Analysis result: Co59.98%, Li7.18%, vibration density 3.56g/cm
3, apparent density 2.8g/cm
3, D50 37.26.
Embodiment 2
A kind of bulky grain high-tap density spherical lithium cobalt synthesis technique, concrete steps are as follows:
(1) solution ratio: get the cobalt salt solution that mass concentration is 1.5mol/L, be diluted to 0.5mol/L with deionized water; Getting sodium carbonate deionized water, to be made into the sodium carbonate liquor of 2.5mol/L concentration for subsequent use;
(2) mixed alkali liquor proportioning: the sodium carbonate liquor of getting by volume step (1) configuration: ammoniacal liquor: the ratio of carbonic hydroammonium 125:1.5:1.2 is mixed, and obtains mixed alkali liquor; Described ammoniacal liquor mass concentration is 2.5mol/L, and carbonic hydroammonium mass concentration is 2.5mol/L;
(3) synthetic: take and flow mode and reactor adds pipe reaction, and continuous pulp discharge;
Concrete steps for: the mixed alkali liquor of getting cobalt salt solution that step (1) configures and step (2) configuration with and the mode of stream before pump, add in reactor; Control step a mixed solution pH value between 7.8; Keep synthesis temperature at 85 DEG C; Control residence time of material at 12h, mixing speed is 120r/min; Circulating pump rotating speed 3200r/min; After finishing, reaction obtains gained spherical cobaltous carbonate; Gained spherical cobaltous carbonate keeps 85 DEG C of precipitation 2h;
(4) dry: get the gained reactant spherical cobaltous carbonate deionized water of 95 DEG C in centrifuge, clean to pH be neutrality, centrifuge speed is 3500r/min, 120 DEG C of oven dry;
(5) calcining: the spherical cobaltous carbonate after drying, at 950 DEG C of calcining 12h, is obtained to cobaltosic oxide;
(6) mix: after the cobaltosic oxide after calcining is directly sieved, then it is mixed according to weight ratio 1.7:1.2 with lithium carbonate or lithium hydroxide;
(7) secondary clacining: the material after mixing, at 950 DEG C of temperature lower calcination 12h, is then sieved and can obtain bulky grain high-tap density spherical lithium cobalt.
Described cobalt salt solution is cobalt chloride, cobaltous sulfate or cobalt nitrate solution.
In described step (6), (7), crossing grit number is 250 orders.
Analysis result: Co60.05%, Li7.16%, vibration density 3.50g/cm
3, apparent density 2.79g/cm
3, D50 37.26.
The above-mentioned grit number of crossing is 200 orders.
Embodiment 3
A kind of bulky grain high-tap density spherical lithium cobalt synthesis technique, concrete steps are as follows:
(1) solution ratio: get the cobalt salt solution that mass concentration is 1.2mol/L, be diluted to 0.4mol/L with deionized water; Getting sodium carbonate deionized water, to be made into the sodium carbonate liquor of 2.3mol/L concentration for subsequent use;
(2) mixed alkali liquor proportioning: the sodium carbonate liquor of getting by volume step (1) configuration: ammoniacal liquor: the ratio of carbonic hydroammonium 120:1.2:1 is mixed, and obtains mixed alkali liquor; Described ammoniacal liquor mass concentration is 2.3mol/L, and carbonic hydroammonium mass concentration is 2.3mol/L;
(3) synthetic: take and flow mode and reactor adds pipe reaction, and continuous pulp discharge;
Concrete steps for: the mixed alkali liquor of getting cobalt salt solution that step (1) configures and step (2) configuration with and the mode of stream before pump, add in reactor; Control step a mixed solution pH value between 7.6; Keep synthesis temperature at 83 DEG C; Control residence time of material at 8h, mixing speed is 110r/min; Circulating pump rotating speed 2800r/min; After finishing, reaction obtains gained spherical cobaltous carbonate; Gained spherical cobaltous carbonate keeps 83 DEG C of precipitation 1-2h;
(4) dry: get the gained reactant spherical cobaltous carbonate deionized water of 93 DEG C in centrifuge, clean to pH be neutrality, centrifuge speed is 3000r/min, 110 DEG C of oven dry;
(5) calcining: the spherical cobaltous carbonate after drying, at 900 DEG C of calcining 10h, is obtained to cobaltosic oxide;
(6) mix: after the cobaltosic oxide after calcining is directly sieved, then it is mixed according to weight ratio 1.6:1.1 with lithium carbonate or lithium hydroxide;
(7) secondary clacining: the material after mixing, at 920 DEG C of temperature lower calcination 10h, is then sieved and can obtain bulky grain high-tap density spherical lithium cobalt.
Described cobalt salt solution is cobalt chloride, cobaltous sulfate or cobalt nitrate solution.
In described step (6), (7), crossing grit number is 230 orders.
Claims (3)
1. a bulky grain high-tap density spherical lithium cobalt synthesis technique, is characterized in that concrete steps are as follows:
(1) solution ratio: get the cobalt salt solution that mass concentration is 1-1.5mol/L, be diluted to 0.2-0.5mol/L with deionized water; Getting sodium carbonate deionized water, to be made into the sodium carbonate liquor of 2-2.5mol/L concentration for subsequent use;
(2) mixed alkali liquor proportioning: the sodium carbonate liquor of getting by volume step (1) preparation: ammoniacal liquor: the ratio of carbonic hydroammonium 115-125:1-1.5:0.8-1.2 is mixed, and obtains mixed alkali liquor; Described ammoniacal liquor mass concentration is 2 ~ 2.5mol/L, and carbonic hydroammonium mass concentration is 2-2.5mol/L;
(3) synthetic: take and flow mode and reactor adds pipe reaction, and continuous pulp discharge;
Concrete steps for: the mixed alkali liquor of getting cobalt salt solution that step (1) configures and step (2) preparation with and the mode of stream before pump, add in reactor; Control the pH value of mixed solution between 7.5-7.8; Keep synthesis temperature at 80-85 DEG C; Control residence time of material at 4-12h, mixing speed is 90-120r/min; Circulating pump rotating speed 2400-3200r/min; After finishing, reaction obtains gained spherical cobaltous carbonate; Gained spherical cobaltous carbonate keeps 80-85 DEG C of precipitation 1-2h;
(4) dry: the deionized water of getting 90-95 DEG C of gained reactant spherical cobaltous carbonate in centrifuge, clean to pH be neutrality, centrifuge speed is 2500-3500r/min, 90-120 DEG C of oven dry;
(5) calcining: the spherical cobaltous carbonate after drying, at 850-950 DEG C of calcining 8-12h, is obtained to cobaltosic oxide;
(6) mix: after the cobaltosic oxide after calcining is directly sieved, then it is mixed according to weight ratio 1.5-1.7:1-1.2 with lithium carbonate or lithium hydroxide;
(7) secondary clacining: the material after mixing, at 900-950 DEG C of temperature lower calcination 8-12h, is then sieved and can obtain bulky grain high-tap density spherical lithium cobalt.
2. bulky grain high-tap density spherical lithium cobalt synthesis technique as claimed in claim 1, is characterized in that: described cobalt salt solution is cobalt chloride, cobaltous sulfate or cobalt nitrate solution.
3. bulky grain high-tap density spherical lithium cobalt synthesis technique as claimed in claim 1, is characterized in that: in described step (6), (7), crossing grit number is 200-250 order.
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| CN106673073A (en) * | 2016-12-23 | 2017-05-17 | 荆门市格林美新材料有限公司 | Method for preparing small-particle size large-bulk cobalt carbonate |
| CN109748330B (en) * | 2019-03-15 | 2021-04-06 | 浙江中金格派锂电产业股份有限公司 | Preparation method of high-compaction cobaltosic oxide |
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| US20060073091A1 (en) * | 2004-10-01 | 2006-04-06 | Feng Zou | Process for producing lithium transition metal oxides |
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