CN102502560A - Lithium iron phosphate precursor element control method - Google Patents
Lithium iron phosphate precursor element control method Download PDFInfo
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- CN102502560A CN102502560A CN2011102947801A CN201110294780A CN102502560A CN 102502560 A CN102502560 A CN 102502560A CN 2011102947801 A CN2011102947801 A CN 2011102947801A CN 201110294780 A CN201110294780 A CN 201110294780A CN 102502560 A CN102502560 A CN 102502560A
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- phosphate precursor
- lithium phosphate
- iron phosphate
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- lithium iron
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Abstract
The invention relates to a lithium iron phosphate precursor element control method, which prepares lithium iron phosphate precursor falling into a cyclone separator by adopting a spray-drying process and is characterized in that main element content analysis is carried out on the lithium iron phosphate precursor by an inductively coupled plasma (ICP) emission spectrometer according to the set main element content ratio of the lithium iron phosphate precursor until the main element content ratio of the lithium iron phosphate satisfies the set ratio range. According to the invention, ICP main element analysis is carried out on the lithium iron phosphate precursor prepared by the spray-drying process and the main element ratio is adjusted according to the analysis result, thus the uncontrollable factors of the main elements are eliminated, the batch stability of the lithium iron phosphate precursor is increased, the method is simple and feasible, and lithium iron phosphate obtained after high-temperature sintering of the lithium iron phosphate precursor has high discharge capacity, stable circulating property and better electrochemical performance and is very suitable for large-scale industrial production process.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries technical field, especially relate to a kind of ferric lithium phosphate precursor element control method.
Background technology
A.K.Padhi in 1997 and J.B.Goodenough have at first proposed iron lithium phosphate and can be used as the positive electrode material of lithium ion battery, and have carried out synthetic and chemical property assessment, and primary iron lithium phosphate patent is grasped in the J.B.Goodenough hand.The Chung of MIT in 2002 and Yet-Ming Chiang have delivered high valence ion doped iron phosphate lithium on the Nature publication, improved the 4-6 one magnitude through this conductivity of electrolyte materials of mixing, and should technology also apply for patent simultaneously.And the another one technological approaches that improves specific conductivity is the carbon coating, and this technology is proposed by Fr doctor M.Armand.More than three iron lithium phosphate technology constituted the core technology that present iron lithium phosphate is produced.
During the preparation iron lithium phosphate, generally be prepared into ferric lithium phosphate precursor earlier, again ferric lithium phosphate precursor carried out high temperature sintering and obtain lithium iron phosphate positive material.The preparation method of ferric lithium phosphate precursor is varied, and spray-drying process, solid phase mechanical ball milling method, liquid phase ball milled, sol-gel method, coprecipitation method etc. are arranged.
Spray-drying process can realize the separation of solidliquid mixture well, thereby obtains exsiccant spherical powder material, is widely used in industries such as food, chemical industry.But during with the spray drying method for preparation ferric lithium phosphate precursor, most of powder is collected from cyclonic separator, and few part powder is collected from filter bag, and the powder main element ratio difference that collect at two places is very big.Common way is that the filter bag powder is given it up, and only gets the whirlwind powder as ferric lithium phosphate precursor, makes iron lithium phosphate through high temperature sintering.Because the element of the ferric lithium phosphate precursor that cyclonic separator is collected can not get control, makes iron level usually be lower than normal value, the iron of loss gets in the filter bag, and this is that defective by spray drying technology itself causes.But when batching, add iron by normal amt usually, this causes the ferric lithium phosphate precursor iron deficiency to cause quality unstable, and the iron lithium phosphate that obtains behind this ferric lithium phosphate precursor high temperature sintering contains miscellaneous, and performance is affected.
Summary of the invention
The present invention provides a kind of ferric lithium phosphate precursor element control method for solving the technical problem that exists in the known technology; This method is simple; Can control cyclonic separator and collect the main element in the ferric lithium phosphate precursor; Improve ferric lithium phosphate precursor batch stability, it is miscellaneous to guarantee that the iron lithium phosphate that obtains behind the ferric lithium phosphate precursor high temperature sintering does not have, and performance is good.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is:
A kind of ferric lithium phosphate precursor element control method; Adopt spray drying method for preparation to go out to fall into the ferric lithium phosphate precursor of cyclonic separator; Be characterized in: according to the ferric lithium phosphate precursor main element content ratio of formulating; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the main element content analysis, add the main element of content, satisfy the ratio range of formulation until the main element content ratio of ferric lithium phosphate precursor.
The present invention can also adopt following technical scheme:
Said ferric lithium phosphate precursor main element content is than being lithium: iron: phosphorus=0.95～1.05: 0.95～1.05: 1.
Advantage and positively effect that the present invention has are:
The ferric lithium phosphate precursor that the present invention goes out spray drying method for preparation carries out the analysis of ICP main element; According to analytical results adjustment main element ratio of components, eliminated the main element uncontrollable factor, improved ferric lithium phosphate precursor batch stability; And method is simple; Guarantee high, the stable circulation of the iron lithium phosphate loading capacity that obtains behind the ferric lithium phosphate precursor high temperature sintering, had better electrochemical performance, be fit to very much large-scale commercial process.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, the following examples of giving an example now specify as follows:
A kind of ferric lithium phosphate precursor element control method adopts spray drying method for preparation to go out to fall into the ferric lithium phosphate precursor of cyclonic separator.
Innovative point of the present invention is: according to the ferric lithium phosphate precursor main element content ratio of formulating; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the main element content analysis; Add the main element of content, satisfy the ratio range of formulation until the main element content ratio of ferric lithium phosphate precursor; Said ferric lithium phosphate precursor main element content is than being lithium: iron: phosphorus=0.95～1.05: 0.95～1.05: 1.
Comparative example 1
In the 300L ball mill, add ethanol 90L, add red stone 12.1kg more successively, monometallic 15.7kg, Natural manganese dioxide 29.8g, carbon black 1.8kg with the slurry spraying drying, obtains sphere, the uniform ferric lithium phosphate precursor of size distribution behind the ball milling 2h; Ferric lithium phosphate precursor is placed High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, high temperature sintering 12h, and cooling obtains the ball shape ferric phosphate lithium powder.
Embodiment 1
Prepare ferric lithium phosphate precursor according to comparative example 1; Ferric lithium phosphate precursor main element content mol ratio lithium according to formulation: iron: phosphorus=0.95～1.05: 0.95～1.05: 1; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the analysis of main element content measuring; The result is a lithium: iron: phosphorus=1.04: 0.91: 1, the ferric lithium phosphate precursor main element content of the said formulation of unmet; In ferric lithium phosphate precursor, add red stone 0.7kg; After the stirring; Main element content ratio to ferric lithium phosphate precursor carries out test analysis again, and mol ratio is a lithium as a result: iron: phosphorus=1.04: 1.02: 1, satisfied the ferric lithium phosphate precursor main element content ratio of formulating; The ferric lithium phosphate precursor that will satisfy the said content ratio of formulation again places High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, and high temperature sintering 12h obtains the ball shape ferric phosphate lithium powder after the cooling.
Comparative example 2
In the 300L ball mill, add alcohol 95 L, add red stone 12.1kg more successively, monometallic 15.7kg, Natural manganese dioxide 29.8g, carbon black 1.8kg with the slurry spraying drying, obtains sphere, the uniform ferric lithium phosphate precursor of size distribution behind the ball milling 2h; Ferric lithium phosphate precursor is placed High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, high temperature sintering 12h, and cooling obtains the ball shape ferric phosphate lithium powder.
Embodiment 2
Prepare ferric lithium phosphate precursor according to comparative example 2; Ferric lithium phosphate precursor main element content mol ratio lithium according to formulation: iron: phosphorus=0.95～1.05: 0.95～1.05: 1; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the analysis of main element content measuring; The result is a lithium: iron: phosphorus=1.03: 0.91: 1, the ferric lithium phosphate precursor main element content of the said formulation of unmet; In ferric lithium phosphate precursor, add red stone 0.7kg; After the stirring; Main element content ratio to ferric lithium phosphate precursor carries out test analysis again, and mol ratio is a lithium as a result: iron: phosphorus=1.04: 1.01: 1, satisfied the ferric lithium phosphate precursor main element content ratio of formulating; The ferric lithium phosphate precursor that will satisfy the said content ratio of formulation again places High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, and high temperature sintering 12h obtains the ball shape ferric phosphate lithium powder after the cooling.
Comparative example 3
In the 300L ball mill, add ethanol 100L, add red stone 12.1kg more successively, monometallic 15.7kg, Natural manganese dioxide 29.8g, carbon black 1.8kg with the slurry spraying drying, obtains sphere, the uniform ferric lithium phosphate precursor of size distribution behind the ball milling 2h; Ferric lithium phosphate precursor is placed High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, high temperature sintering 12h, and cooling obtains the ball shape ferric phosphate lithium powder.
Embodiment 3
Prepare ferric lithium phosphate precursor according to comparative example 3; Ferric lithium phosphate precursor main element content mol ratio lithium according to formulation: iron: phosphorus=0.95～1.05: 0.95～1.05: 1; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the analysis of main element content measuring; The result is a lithium: iron: phosphorus=1.03: 0.86: 1, the ferric lithium phosphate precursor main element content of the said formulation of unmet; In ferric lithium phosphate precursor, add red stone 0.7kg; After the stirring; Main element content ratio to ferric lithium phosphate precursor carries out test analysis again, and mol ratio is a lithium as a result: iron: phosphorus=1.04: 1.01: 1, satisfied the ferric lithium phosphate precursor main element content ratio of formulating; The ferric lithium phosphate precursor that will satisfy the said content ratio of formulation again places High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, and high temperature sintering 12h obtains the ball shape ferric phosphate lithium powder after the cooling.
Comparative example 4
In the 300L ball mill, add ethanol 105L, add red stone 12.1kg more successively, monometallic 15.7kg, Natural manganese dioxide 29.8g, carbon black 1.8kg with the slurry spraying drying, obtains sphere, the uniform ferric lithium phosphate precursor of size distribution behind the ball milling 2h; Ferric lithium phosphate precursor is placed High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, high temperature sintering 12h, and cooling obtains the ball shape ferric phosphate lithium powder.
Embodiment 4
Prepare ferric lithium phosphate precursor according to comparative example 4; Ferric lithium phosphate precursor main element content mol ratio lithium according to formulation: iron: phosphorus=0.95～1.05: 0.95～1.05: 1; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the analysis of main element content measuring; The result is a lithium: iron: phosphorus=1.03: 0.91: 1, the ferric lithium phosphate precursor main element content of the said formulation of unmet; In ferric lithium phosphate precursor, add red stone 0.7kg; After the stirring; Main element content ratio to ferric lithium phosphate precursor carries out test analysis again, and mol ratio is a lithium as a result: iron: phosphorus=1.03: 0.99: 1, satisfied the ferric lithium phosphate precursor main element content ratio of formulating; The ferric lithium phosphate precursor that will satisfy the said content ratio of formulation again places High Temperature Furnaces Heating Apparatus, and the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, and high temperature sintering 12h obtains the ball shape ferric phosphate lithium powder after the cooling.
Table 1 listed different embodiment and comparative example presoma icp analysis result and the iron lithium phosphate that these presomas obtain after pyroprocessing performance relatively.
The presoma icp analysis of different embodiment of table 1 and comparative example and presoma warp
The performance of the iron lithium phosphate that obtains after the pyroprocessing relatively
Can find out that from the result of table 1 more reasonable through the ferric lithium phosphate precursor main element ratio of the present invention's preparation, presoma is high through the iron lithium phosphate loading capacity that obtains after the pyroprocessing, stable circulation, has better electrochemical performance.
Claims (2)
1. ferric lithium phosphate precursor element control method; Adopt spray drying method for preparation to go out to fall into the ferric lithium phosphate precursor of cyclonic separator; It is characterized in that: according to the ferric lithium phosphate precursor main element content ratio of formulating; With the inductively coupled plasma emission spectrometer said ferric lithium phosphate precursor is carried out the main element content analysis, add the main element of content, satisfy the ratio range of formulation until the main element content ratio of ferric lithium phosphate precursor.
2. ferric lithium phosphate precursor element control method according to claim 2 is characterized in that: said ferric lithium phosphate precursor main element content is than being lithium: iron: phosphorus=0.95～1.05: 0.95～1.05: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101789507A (en) * | 2009-01-22 | 2010-07-28 | 韩华石油化学株式会社 | Electrode active material for anion-deficient lithium transition metal phosphate compound, method of preparing same, and electrochemical device using same |
| CN101847763A (en) * | 2010-04-09 | 2010-09-29 | 奇瑞汽车股份有限公司 | Comprehensive recovering method of waste lithium iron phosphate battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101789507A (en) * | 2009-01-22 | 2010-07-28 | 韩华石油化学株式会社 | Electrode active material for anion-deficient lithium transition metal phosphate compound, method of preparing same, and electrochemical device using same |
| CN101847763A (en) * | 2010-04-09 | 2010-09-29 | 奇瑞汽车股份有限公司 | Comprehensive recovering method of waste lithium iron phosphate battery |
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Application publication date: 20120620 |