CN105129760A - Wet chemical method of preparing manganese iron lithium phosphate through polyhydroxyl solvothermal method - Google Patents
Wet chemical method of preparing manganese iron lithium phosphate through polyhydroxyl solvothermal method Download PDFInfo
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Abstract
The invention relates to a wet chemical method of preparing manganese iron lithium phosphate through a polyhydroxyl solvothermal method and belongs to the technical field of inorganic new energy materials. The wet chemical method comprises following steps: 1) liquid phase synthesis: filling a reactor with a template agent and water, feeding nitrogen to dispel the residual air in the reactor, heating the reactor to 110-150 DEG C, adding a mixed solution of ferrite and manganate to generate a white precipitate, adding a lithium phosphate solution to carry out a reaction, and when the color of the system is turned from white into grey-green, filtering the precipitation, washing the precipitation with a washing agent to obtain a grey-green precipitation; and 2) thermal treatment: moving the grey-green precipitation into an atmosphere furnace, and roasting the grey-green precipitation under protection of nitrogen gas to obtain a grey-black product. The wet chemical method is relative loose in process, is simple in parameter controlling and is free of a special high-pressure device and allows the raw materials to be mixed uniformly. The product is stable in quality and is excellent in physical property indexes and electromagnetic performances.
Description
Technical field
The invention belongs to inorganic novel energy resource material technology field, particularly relate to a kind of wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium.
Background technology
At present, iron manganese phosphate lithium material generally adopts liquid process to synthesize, namely raw material is through solid phase mixing ball milling, low temperature presintering (300-500 DEG C), secondary ball milling and high temperature pre-burning operation (600-750 DEG C), finally obtain product, there is lot stability difference in liquid process, quality fluctuation is large waits series of problems, and two-step sintering energy consumption is higher simultaneously, causes the further increase of production cost.
Chinese patent 201210252888.9 discloses a kind of preparation method of lithium iron manganese phosphate cathode composite material, 1) the lithium source got ready, ferric iron source, Manganse Dioxide, phosphorus source and carbon source are put in ball grinder, add dispersion agent and complexing agent, then ball milling on ball mill, grind again after oven dry, obtain LiMnxFe1-xPO4 presoma; 2) presoma is put into calcining furnace, pass into rare gas element as shielding gas, then heat with the temperature rise rate of 1-8 DEG C, when being heated to 400-750 DEG C, constant temperature 6-12h, then naturally cools to room temperature, obtains lithium iron manganese phosphate cathode composite material.
The technique of another kind of synthesis iron manganese phosphate for lithium is hydrothermal method, although hydrothermal method to some extent solves consistency problem, to equipment requirements harshness (the high pressure resistant equipment of general needs), production cost is higher.
Chinese patent 201410039404.1 discloses a kind of hydrothermal preparing process of nano lithium iron manganese phosphate anode material.Prepare precursor: Li:P=3:1 is by H3PO4 solution and lithium hydroxide mixing in molar ratio; Add strong aqua, pH value 9 ~ 10; Be warming up to 180 DEG C, (Fe+Mn): Ti:P=0.99:0.01:1 adds in deionized water in molar ratio, and mixing solutions pumps in reactor, and regulating and controlling temperature is at 170 ~ 200 DEG C; Be heated to 200 DEG C of insulations 7 ~ 10 hours; Again washing and carbon coated: when being cooled to less than 60 DEG C, with deionized water wash to sulfate radical-free, add dissolved organic matter carbon source, spraying dry, thermal treatment 7 ~ 10 hours, obtains LiMnxFe0.99-xTi0.01PO4 powder after cooling.These class methods in fact also be unable to do without follow-up high temperature sintering, and energy consumption reduction has little significance.
Summary of the invention
The present invention provides a kind of wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium for solving in known technology the technical problem that exists.
The object of the invention is the problem such as complex process, equipment harshness of quality consistency difference and the hydrothermal synthesis method existence come out for iron manganese phosphate for lithium solid phase production technique, a kind of wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium is provided.The method utilizes liquid reactive homogeneity, by controlling concrete technology parameter, in achieving batch and batch between quality stable.In addition, because liquid phase reaction is carried out under normal pressure, the use of specific installation is avoided.
The method of the invention feature is main raw material ferrous salt, manganese salt and phosphoric acid lithium salts feed intake according to mol ratio 1:1, raw material availability 100% (reclaiming without the need to lithium), iron manganese phosphate for lithium generates in liquid phase in addition, the heat treated object of short period of time low-temperature sintering is to realize regular crystal forms, and therefore heat treated temperature, time are reduced all greatly.
The technical scheme that the present invention utilizes the wet chemical method of polyhydroxyl solvents hot preparation iron manganese phosphate for lithium to take is:
Utilize a wet chemical method for polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, it is characterized in that: utilize the wet chemical method of polyhydroxyl solvents hot preparation iron manganese phosphate for lithium to comprise following processing step:
1. liquid phase synthesis
Template and water are dropped into reactor, passes into nitrogen and drain air residual in system, be heated to 110-150 DEG C of temperature; The mixing solutions adding ferrous salt and manganese salt produces white precipitate, and add the reaction of Trilithium phosphate salts solution, system color fades to greyish-green by white, by sedimentation and filtration, with detergent washing, obtains greyish-green precipitation;
Template be ethylene glycol, glycol ether, polyoxyethylene glycol one or more, be preferably glycol ether; Ferrous salt be Ferrox, ferrous sulfate, iron protochloride one or more, be preferably ferrous sulfate; Manganese salt be manganous sulfate, manganous acetate, Manganous chloride tetrahydrate one or more, be preferably manganous acetate; Phosphoric acid lithium salts be monometallic, phosphoric acid hydrogen two lithium, tricresyl phosphate lithium one or more, be preferably monometallic; Passing into the time that nitrogen drains air is 1-2 hour, is preferably 1 hour;
2. thermal treatment
Move in atmosphere furnace by greyish-green precipitation, roasting obtains grey black product under nitrogen protection.
The present invention utilizes the wet chemical method of polyhydroxyl solvents hot preparation iron manganese phosphate for lithium can also adopt following technical scheme:
The described wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, is characterized in: during liquid phase synthesis, and the volume ratio of template and water is 2-4:1, is preferably 3:1.
The described wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, be characterized in: during liquid phase synthesis, the mixing solutions total concn of ferrous salt and manganese salt is 2mol/L, and Trilithium phosphate concentration of salt solution is 2mol/L, and Trilithium phosphate salts solution adopts dropping mode to be added in white precipitate.
The described wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, is characterized in: Trilithium phosphate salts solution time for adding is 0.5-1.5 hour, is preferably 1 hour; It is 2-6 hour that dropping terminates the rear continuation reaction times, is preferably 4 hours.
The described wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, is characterized in: during thermal treatment, and the temperature of roasting is 400-550 DEG C, preferred 450-500 DEG C, and roasting time is 2-4 hour, is preferably 3 hours.
The advantage that the present invention has and positively effect are:
Utilize the wet chemical method of polyhydroxyl solvents hot preparation iron manganese phosphate for lithium owing to have employed the brand-new technical scheme of the present invention, compared with prior art, synthesis technique relative loose of the present invention, parameter is easy to control and mix without the need to each raw material of special high-tension apparatus, and physical index and the chemical property of product are good.
Accompanying drawing explanation
Fig. 1 is that embodiment of the present invention preparation method obtains sample first charge-discharge curve;
Fig. 2 is that embodiment of the present invention preparation method obtains cycles samples performance curve;
Fig. 3 is that embodiment of the present invention preparation method obtains sample SEM photo (a: embodiment 3, b: embodiment 2, c: embodiment 1);
Fig. 4 is that the present invention compares preparation method and obtains cycles samples performance curve.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
Accompanying drawings 1 to Fig. 4.
Embodiment 1
Utilize a wet chemical method for polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, its technological process: be fed in reactor by 350ml ethylene glycol and 100ml water, pass into nitrogen 1 hour, to drain air residual in system, be then warming up to 120 DEG C; Ferrous sulfate and the manganous acetate mixing solutions 50ml (mol ratio of iron and manganese is 1:4) of 2mol/L is added after temperature-stable, produce white precipitate immediately, prepare the Trilithium phosphate salts solution 50ml of 2mol/L and drop in above-mentioned white precipitate, time for adding is 1 hour, drips after terminating, keep temperature-resistant, continue reaction 3 hours, system color fades to greyish-green by white, by sedimentation and filtration, and use detergent washing 3 times, obtain greyish-green precipitation; Washing composition is the mixed solution of deionized water, glycol ether and ethanol, and dose volume is 2:1:1; This greyish-green precipitation is moved in atmosphere furnace, under nitrogen protection in 500 DEG C of roastings 3 hours, obtains grey black product.
Positive active material, conductive agent (acetylene black) and polyvinylidene difluoride (PVDF) (PVDF) caking agent are compared Homogeneous phase mixing by the quality of 90:5:5, be dissolved in solvent N-methyl pyrilidone (NMP), be uniformly mixed, vacuumize the gas in the mixed slurry of removing, be evenly coated on 20 μm of thick aluminium foils, dry at 100 DEG C, roll under 15MPa pressure, being die-cut into diameter with circle is that the disk of 20mm is as positive plate.
Ready-made positive plate is placed in vacuum drying oven, stays for subsequent use at 80 DEG C after more than vacuum-drying 12h.Be to electrode with metal lithium sheet, diameter is 24mm, and thickness is 0.30mm, and compared with positive active material, the consumption of cathode of lithium is superfluous.20 μm of thick, diameters are adopted to be 28mmCelgard barrier film.Electrolytic solution adopts 1mol/LLiPF6, the solvent mixed solution of NSC 11801 (EC) and dimethyl carbonate (DMC) (mass ratio 1:1).Be less than in 5ppm drying room at moisture and be assembled into CR2430 type button cell, to be tested after leaving standstill 12h.
Embodiment 2
Utilize a wet chemical method for polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, its technological process: be fed in reactor by 300ml ethylene glycol and 100ml water, pass into nitrogen 1.5 hours, to drain air residual in system, be then warming up to 140 DEG C; Ferrous sulfate and the manganous acetate mixing solutions 50ml (mol ratio of iron and manganese is 1:1) of 2mol/L is added after temperature-stable, produce white precipitate immediately, prepare the Trilithium phosphate salts solution 50ml of 2mol/L and drop in above-mentioned white precipitate, time for adding is 1 hour, drips after terminating, keep temperature-resistant, continue reaction 4 hours, system color fades to greyish-green by white, by sedimentation and filtration, and use detergent washing 3 times, obtain greyish-green precipitation; Washing composition is the mixed solution of deionized water, glycol ether and ethanol, and dose volume is 2:1:1; This greyish-green precipitation is moved in atmosphere furnace, under nitrogen protection in 400 DEG C of roastings 4 hours, obtains grey black product.(as follows embodiment 1)
Embodiment 3
Utilize a wet chemical method for polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, its technological process: be fed in reactor by 200ml glycol ether and 100ml water, pass into nitrogen 2 hours, to drain air residual in system, be then warming up to 160 DEG C; Ferrous sulfate and the manganous acetate mixing solutions 50ml (mol ratio of iron and manganese is 4:1) of 2mol/L is added after temperature-stable, produce white precipitate immediately, prepare the Trilithium phosphate salts solution 50ml of 2mol/L and drop in above-mentioned white precipitate, time for adding is 1.5 hours, drips after terminating, keep temperature-resistant, continue reaction 2 hours, system color fades to greyish-green by white, by sedimentation and filtration, and use detergent washing 3 times, obtain greyish-green precipitation; Washing composition is the mixed solution of deionized water, glycol ether and ethanol, and dose volume is 2:1:1; This greyish-green precipitation is moved in atmosphere furnace, under nitrogen protection in 450 DEG C of roastings 3 hours, obtains grey black product.(as follows embodiment 1)
Comparative example 1
By Ferrox, manganous carbonate, monometallic, dextrose anhydrous according to Li:Mn:Fe:P:C=1:0.8:0.2:1:0.3 (mol ratio); be fed in ball mill; using acetone as ball-milling medium; ball milling 4 hours; then slurry good for ball milling is carried out spraying dry at 160 DEG C, dried sample, under argon shield, 350 DEG C sinter 7 hours; then powder continues ball milling 2 hours, and finally at 650 DEG C, sintering obtains the finished product in 12 hours.
Claims (5)
1. utilize a wet chemical method for polyhydroxyl solvents hot preparation iron manganese phosphate for lithium, it is characterized in that: utilize the wet chemical method of polyhydroxyl solvents hot preparation iron manganese phosphate for lithium to comprise following processing step:
(1) liquid phase synthesis
Template and water are dropped into reactor, passes into nitrogen and drain air residual in system, be heated to 110-150 DEG C of temperature; The mixing solutions adding ferrous salt and manganese salt produces white precipitate, and add the reaction of Trilithium phosphate salts solution, system color fades to greyish-green by white, by sedimentation and filtration, with detergent washing, obtains greyish-green precipitation;
Template be ethylene glycol, glycol ether, polyoxyethylene glycol one or more, be preferably glycol ether; Ferrous salt be Ferrox, ferrous sulfate, iron protochloride one or more, be preferably ferrous sulfate; Manganese salt be manganous sulfate, manganous acetate, Manganous chloride tetrahydrate one or more, be preferably manganous acetate; Phosphoric acid lithium salts be monometallic, phosphoric acid hydrogen two lithium, tricresyl phosphate lithium one or more, be preferably monometallic;
(2) thermal treatment
Move in atmosphere furnace by greyish-green precipitation, roasting obtains grey black product under nitrogen protection.
2. the wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium according to claim 1, is characterized in that: during liquid phase synthesis, and the volume ratio of template and water is 2-4:1, is preferably 3:1.
3. the wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium according to claim 1 and 2, it is characterized in that: during liquid phase synthesis, the mixing solutions total concn of ferrous salt and manganese salt is 2mol/L, Trilithium phosphate concentration of salt solution is 2mol/L, and Trilithium phosphate salts solution adopts dropping mode to be added in white precipitate.
4. the wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium according to claim 3, is characterized in that: Trilithium phosphate salts solution time for adding is 0.5-1.5 hour, is preferably 1 hour; It is 2-6 hour that dropping terminates the rear continuation reaction times, is preferably 4 hours.
5. the wet chemical method utilizing polyhydroxyl solvents hot preparation iron manganese phosphate for lithium according to claim 1, is characterized in that: during thermal treatment, and the temperature of roasting is 400-550 DEG C, preferred 450-500 DEG C, and roasting time is 2-4 hour, is preferably 3 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101777648A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of monodisperse lithium iron phosphate nanometer material and lithium-ion secondary battery |
| CN101973540A (en) * | 2010-11-18 | 2011-02-16 | 中国海洋石油总公司 | Process method for preparing lithium iron phosphate by polyhydroxy solvent wet heating method |
| CN103515578A (en) * | 2013-07-15 | 2014-01-15 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery anode material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101777648A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of monodisperse lithium iron phosphate nanometer material and lithium-ion secondary battery |
| CN101973540A (en) * | 2010-11-18 | 2011-02-16 | 中国海洋石油总公司 | Process method for preparing lithium iron phosphate by polyhydroxy solvent wet heating method |
| CN103515578A (en) * | 2013-07-15 | 2014-01-15 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery anode material |
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Application publication date: 20151209 |