CN105668643A - Method for preparing lithium ion batteries cathode material - Google Patents
Method for preparing lithium ion batteries cathode material Download PDFInfo
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- CN105668643A CN105668643A CN201610019355.4A CN201610019355A CN105668643A CN 105668643 A CN105668643 A CN 105668643A CN 201610019355 A CN201610019355 A CN 201610019355A CN 105668643 A CN105668643 A CN 105668643A
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Abstract
The invention discloses a method for preparing a lithium ion batteries cathode material. The method comprises the following steps: 1) refining ferrous sulfate heptahydrate crystal grains; 2) performing ultrasonic microwave processing on a reactant ferrous sulfate heptahydrate and lithium fluoride; 3) heating a reaction vessel with controlled temperature; and 4) processing products. According to the invention, a reaction system is introduced into an ultrasonic microwave combination reaction system, synergistic effect of supersonic wave and microwave can be fully performed, dispersion of the reactant by a surfactant and control of the resultant morphology can be promoted, the method has the advantages of simple process and high efficiency, and is in favor of industrial production and practical production popularization of the material. Compared with the material by employing a solvent method, the LiFeSO4F of the prepared lithium ion batteries cathode material has high higher electrochemistry capacity which can reach 90% of a theoretical discharge capacity of the LiFeSO4F.
Description
Technical field
The invention belongs to technical field of lithium ion, the preparation method being specifically related to a kind of anode material for lithium-ion batteries.
Background technology
Along with the innovation that lithium ion battery technology is rapid, lithium electric automobile obtains development energetically and popularization. The Vehicular battery of electric automobile requires to have higher energy density, good cycle performance, permanent service life, the security performance of excellence, structural stability etc. Positive electrode, negative material, battery diaphragm, electrolyte are the important component parts of lithium ion battery, wherein positive electrode is maximum to the decisive role of the energy density of battery, studies interest greatly because all anode material for lithium-ion batteries being had inside and outside the industry. At present, the positive electrode that market share is leading in lithium electric automobile market is LiFePO4 (LiFePO4), LiMn2O4 (LiMn2O4), ternary material (LiNiaMnbXcOd, X=Co, Al etc.), cobalt acid lithium (LiCoO2), wherein LiFePO4 is with low cost with it, resource is easy to get, good cycle performance and cycle performance, it is thus achieved that the accreditation of lithium electricity electric motor car industry experts and the favor of numerous power car manufacturers.
LiFePO4 (LiFePO4Although) it is considered as the positive electrode of current driving force car Battery Market great potential, but this material undeniable still suffers from many weak points, such as relatively low electronic conductivity, therefore to industrialized production, its electrical conductivity must be improved reach industrial requirements by nanorize and carbon cladding in prepared by material, and this can increase the complexity of overall production cost and preparation, it is unfavorable for popularization and the use of material.
Sulphuric acid fluorine ferrum lithium (LiFeSO4F) it is a kind of novel anode material for lithium-ion batteries grown up on the basis of LiFePO 4 of anode material, on " nature " magazine, just caused the concern of whole world lithium electricity positive electrode scholar in 2009 once report. Compared to lithium iron phosphate positive material, although sulphuric acid fluorine ferrum lithium material theoretical capacity is lower slightly, but because of its slightly higher charge and discharge platform, and superior electronic conductivity, make the strong substitution material of LiFePO4.
Sulphuric acid fluorine ferrum lithium has monocline and three oblique two kinds of crystal formations, and the method for the sulphuric acid fluorine ferrum lithium preparing monoclinic form at present mainly has ion full-boiled process, solvent-thermal method, microwave method, discharge plasma sintering method.But, the reaction medium of ion full-boiled process be expensive and and ionic liquid not environmentally, be not suitable for industrialized production; Solvent-thermal method many employings environmental protection, the polymerization alcohols that can be recycled, as reaction medium, are beneficial to industrialization large-scale production.
Summary of the invention
For solving the shortcoming and defect part of prior art, the preparation method that it is an object of the invention to provide a kind of anode material for lithium-ion batteries. The method is a kind of ultrasonic-microwave secondary solvent full-boiled process, surface chemistry from reaction, by the synergism of microwave ultrasound, make surfactant control dispersion and the growth of crystal grain in material preparation in microcosmic point, prepare the target product sulphuric acid fluorine ferrum lithium with unique morphology electrochemical performance.
The object of the invention is achieved through the following technical solutions:
The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:
(1) grain refinement of ferrous sulfate heptahydrate: ferrous sulfate heptahydrate and citric acid are dissolved in deionized water, stirring is lower adds appropriate dehydrated alcohol, obtains mixture vacuum filtration precipitating out solid, vacuum drying, the ferrous sulfate heptahydrate after being refined;
(2) ultrasonic-microwave of reactant ferrous sulfate heptahydrate and lithium fluoride processes: under inert gas atmosphere, in tetraethylene glycol (TEG) medium, add the ferrous sulfate heptahydrate after the refinement prepared in appropriate step (1), lithium fluoride and dodecylbenzene sodium sulfonate (SDBS), carry out ultrasonic-microwave heating;
(3) reactor temperature programmed control heating: the uniform mixture after step (2) having been processed moves in high-temperature high-pressure reaction kettle, and completes seal operation under inert gas atmosphere, and high-temperature high-pressure reaction kettle is heated;
(4) product processes: when high-temperature high-pressure reaction kettle is cooled to room temperature, take out wherein mixture, centrifugal, and washs with dichloromethane, last vacuum drying, obtains anode material for lithium-ion batteries.
The mass ratio of step (1) described ferrous sulfate heptahydrate and citric acid is 10:1.
The described vacuum drying temperature of step (1) is 35～40 DEG C.
Ferrous sulfate heptahydrate and the mol ratio of lithium fluoride after step (2) described refinement are 1:1.15, and described dodecylbenzene sodium sulfonate mass fraction is 0.2～1% (by total system quality).
The described tetraethylene glycol (TEG) medium of step (2) is preferably analytical pure tetraethylene glycol (TEG).
The program of the described ultrasonic-microwave heating of step (2) is set to: exploration type brute force sonication stage time 2～3s, the ultrasonic 1s that is spaced apart, and total ultrasonic time is set to 2～3h; Microwave heating power setting is 50～100w, and temperature is set to 90 DEG C, and set of time is 2～3h. Have employed ultrasonic-microwave composite reaction system, by controlling ultrasonic interval time, ultrasonic time, control power and the time of microwave heating simultaneously, to promote the surfactant peptizaiton on reactant and the impact on crystal growth.
Noble gas described in step (2) and step (3) is preferably nitrogen.
The program of step (3) described heating is set to: is raised to 230～280 DEG C with the heating rate of 1 DEG C/min, and keeps 2～5d at such a temperature; In heating process, device is in static condition, without stirring.
The described vacuum drying temperature of step (4) is 80 DEG C, and the time is 4h.
The synthetic reaction of anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium, is actually a topology reaction, and reactant is ferrous sulfate heptahydrate (FeSO4·7H2And lithium fluoride (LiF) O), last molecular water of ferrous sulfate heptahydrate is sloughed, and lithium fluoride addition process on anhydrous slufuric acid ferrous iron is the committed step of reaction simultaneously.In the present invention, we select ultrasonic-microwave secondary solvent full-boiled process, promote the anionic surfactant sodium dodecylbenzene sulfonate (SDBS) dispersion to reactant, adjusting and controlling growth effect with crystal, achieve the pattern controlling product anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium from microcosmic angle, and it is effectively improved the chemical property of anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium, be conducive to industrialized production to apply.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The preparation method of anode material for lithium-ion batteries of the present invention, reaction system is incorporated in ultrasonic-microwave composite reaction system, give full play to the synergism of ultrasound wave and microwave, promote the control of the surfactant dispersion to reactant and product pattern, method simple and effective, is conducive to the industrialized production of material and actual production to promote.
The preparation method of anode material for lithium-ion batteries of the present invention, the anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium prepared, this material adopting solvent method to prepare more equally, has higher electrochemistry capacitance, can reach the 92% of sulphuric acid fluorine ferrum lithium material theoretical discharge capacity.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet prepared by the anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium of the present invention.
Fig. 2 is the charge/discharge capacity figure of anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium prepared by the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium prepared by the present invention.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical. Technical term used herein is intended merely to the purpose describing specific embodiment, is not intended to limit the scope of the invention.
Except there being specified otherwise, various reagent, the raw material used in the present invention are and maybe can pass through the product that known method prepares by commodity commercially.
Embodiment 1
A kind of preparation method of anode material for lithium-ion batteries, as it is shown in figure 1, comprise the following steps:
(1) ferrous sulfate heptahydrate (FeSO4·7H2O) grain refinement: ferrous sulfate heptahydrate and citric acid that mass ratio is 10:1 are dissolved in a certain amount of deionized water, appropriate dehydrated alcohol is poured on magnetic agitation limit, limit in solution, obtain mixture vacuum filtration precipitating out solid, and at the dry 0.5h of 35 DEG C of vacuum drying ovens, the ferrous sulfate heptahydrate after being refined;
(2) ultrasonic-microwave of reactant ferrous sulfate heptahydrate and lithium fluoride (LiF) processes: in a nitrogen atmosphere, the ferrous sulfate heptahydrate after the refinement prepared in appropriate step (1) and lithium fluoride (mol ratio is 1:1.15) is added in analytical pure tetraethylene glycol (TEG) medium, and the dodecylbenzene sodium sulfonate (SDBS) that mass fraction is 0.2% (by total system quality), carry out ultrasonic-microwave heating; Ultrasonic-microwave heating process is arranged: the powerful ultrasonic sonication stage time 3s that is set to of exploration type, ultrasonic is spaced apart 1s; The temperature of microwave heating process is set to 90 DEG C, and set of time is 3h, and power setting is 50w;
(3) reactor temperature programmed control heating: the uniform mixture after ultrasonic is moved in high-temperature high-pressure reaction kettle, and complete seal operation in a nitrogen atmosphere, program that reactor is heated is arranged: is raised to 260 DEG C with the heating rate of 1 DEG C/min, and keeps 3d at such a temperature;In heating process, device is in static condition, without stirring.
(4) product processes: when question response still naturally cools to room temperature, take out wherein mixture, centrifugal, and washs with dichloromethane, finally places dry 4h in 80 DEG C of vacuum drying ovens, obtains anode material for lithium-ion batteries.
The charging and discharging curve of anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium prepared by the present invention is as shown in Figure 2. When 0.05c, the button cell assembling and standing activation being carried out charge-discharge test, charge-discharge test includes constant-current charge, constant-voltage charge, constant-current discharge three phases. The specific discharge capacity of electrode material sulphuric acid fluorine ferrum lithium can reach 135mAh/g, close to this materials theory capacity (150mAh/g) 90%, charging capacity and the discharge capacity of material are close, show higher coulombic efficiency, also demonstrate that the excellent electrochemical performance of sulphuric acid fluorine ferrum lithium material prepared by the method.
The scanning electron microscope (SEM) photograph (SEM) of anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium prepared by the present invention is as shown in Figure 3. The material list of synthesis reveals the surface topography of the class Semen Juglandis of uniqueness, and this pattern can be effectively improved the contact area of material and electrolyte, is conducive to accelerating the transmission of electronics and ion, reduces the reaction resistance of material, plays excellent chemical property.
Embodiment 2
The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:
(1) grain refinement of ferrous sulfate heptahydrate: ferrous sulfate heptahydrate and citric acid that mass ratio is 10:1 are dissolved in a certain amount of deionized water, appropriate dehydrated alcohol is poured on magnetic agitation limit, limit in solution, obtain mixture vacuum filtration precipitating out solid, and at the dry 0.5h of 35 DEG C of vacuum drying ovens, the ferrous sulfate heptahydrate after being refined;
(2) ultrasonic-microwave of reactant ferrous sulfate heptahydrate and lithium fluoride processes: in a nitrogen atmosphere, the ferrous sulfate heptahydrate after the refinement prepared in appropriate step (1) and lithium fluoride (mol ratio is 1:1.15) is added in analytical pure tetraethylene glycol (TEG) medium, and the dodecylbenzene sodium sulfonate (SDBS) that mass fraction is 0.4% (by total system quality), carry out the ultrasonic-microwave heating of different capacity; Ultrasonic-microwave heating process is arranged: the powerful ultrasonic sonication stage time 3s that is set to of exploration type, ultrasonic is spaced apart 1s; The temperature of microwave heating process is set to 90 DEG C, and set of time is 3h, and power setting is 80w;
(3) reactor temperature programmed control heating: the uniform mixture after ultrasonic is moved in high-temperature high-pressure reaction kettle, and complete seal operation in a nitrogen atmosphere, program that reactor is heated is arranged: is raised to 260 DEG C with the heating rate of 1 DEG C/min, and keeps 3d at such a temperature. In heating process, device is in static condition, without stirring;
(4) product processes: when question response still naturally cools to room temperature, take out wherein mixture, centrifugal, and washs with dichloromethane, finally places dry 4h in 80 DEG C of vacuum drying ovens, obtains anode material for lithium-ion batteries.
Embodiment 3
The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:
(1) grain refinement of ferrous sulfate heptahydrate: ferrous sulfate heptahydrate and citric acid that mass ratio is 10:1 are dissolved in a certain amount of deionized water, appropriate dehydrated alcohol is poured on magnetic agitation limit, limit in solution, obtain mixture vacuum filtration precipitating out solid, and at the dry 0.5h of 35 DEG C of vacuum drying ovens, the ferrous sulfate heptahydrate after being refined;
(2) ultrasonic-microwave of reactant ferrous sulfate heptahydrate and lithium fluoride processes: in a nitrogen atmosphere, the ferrous sulfate heptahydrate after the refinement prepared in appropriate step (1) and lithium fluoride (mol ratio is 1:1.15) is added in analytical pure tetraethylene glycol (TEG) medium, and the dodecylbenzene sodium sulfonate (SDBS) that mass fraction is 0.6% (by total system quality), carry out the ultrasonic-microwave heating of different capacity;Ultrasonic-microwave heating process is arranged: the powerful ultrasonic sonication stage time 2s that is set to of exploration type, ultrasonic is spaced apart 1s; The temperature of microwave heating process is set to 90 DEG C, and set of time is 2h, and power setting is 100w;
(3) reactor heating: the uniform mixture after ultrasonic is moved in high-temperature high-pressure reaction kettle, and complete seal operation in a nitrogen atmosphere, program that reactor is heated is arranged: is raised to 260 DEG C with the heating rate of 1 DEG C/min, and keeps 3d at such a temperature; In heating process, device is in static condition, without stirring;
(4) product processes: when question response still naturally cools to room temperature, take out wherein mixture, centrifugal, and washs with dichloromethane, finally places dry 4h in 80 DEG C of vacuum drying ovens, obtains anode material for lithium-ion batteries.
Comparative example 1: namely usual vehicle full-boiled process prepares lithium ion anode material sulphuric acid fluorine ferrum lithium.
(1) ferrous sulfate monohydrate (FeSO4·H2O) preparation: by the ferrous sulfate heptahydrate (FeSO of certain mass4·7H2O) (medicine directly bought) heats 2～3h at the vacuum drying ovens of 100 DEG C, obtains the ferrous sulfate monohydrate after dehydration.
(2) dispersion in the solution of ferrous sulfate monohydrate and lithium fluoride processes: ferrous sulfate monohydrate and lithium fluoride added in tetraethylene glycol (TEG) medium with mol ratio for 1:1.15, and adopts stirring or extraneous ultrasonic disperse.
(3) reactor heating: being moved in high-temperature high-pressure reaction kettle by finely dispersed mixture, placed in baking oven by reactor and be heated, heating-up temperature is 260 DEG C, and keeps 2～5d at such a temperature.
(4) product processes: when question response still naturally cools to room temperature, take out wherein mixture, centrifugal, and washs with dichloromethane, finally places dry 4h in 80 DEG C of vacuum drying ovens, obtains anode material for lithium-ion batteries.
Respectively by anode material for lithium-ion batteries and the acetylene black of preparation in above-described embodiment 1-3 and comparative example 1, Vingon (PVDF) with the ratio precise of 7:2:1, standby. First being put into by PVDF in dried clean agate jar, add a small amount of NMP, stirring makes the fluid of clear homogeneous, then will grind uniform graphite in advance and acetylene black mixture adds ball milling 6h in agate jar; Utilize scraper, the slurry obtained is applied to uniformly on the Cu paper tinsel cleaned up in advance after ball milling, then 120 DEG C of dry 24h, it is cut into, with microtome, the sequin that diameter is 12mm after dried pole piece compacting, vacuum drying is standby.
Experiment adopts CR2025 type button cell, and battery is at the glove box (H of full argon2O < 2PPM, O2< 2PPM) middle assembling. Smear pole piece is positive pole, and metal lithium sheet is negative pole, and barrier film adopts Celgard2300, and electrolyte selects LiPF6(EC:DMC=1:1). Stand 10h after being taken out from glove box by button cell and be used for other tests. Room temperature loop test operates: in 2.5～4.2V voltage range, battery is carried out the discharge and recharge under 0.05c multiplying power. Test instrunment is constant current charge-discharge instrument (Shenzhen Xin Wei company limited). Test result is as shown in table 1.
The performance test results contrast of the anode material for lithium-ion batteries of table 1 embodiment 1-3 and comparative example 1 preparation
As can be known from Table 1, preparation for anode material for lithium-ion batteries sulphuric acid fluorine ferrum lithium, ultrasonic-microwave auxiliary law relatively usual vehicle full-boiled process has greater advantage, change regardless of power and time, this material prepared by ultrasonic-microwave auxiliary law has higher theoretical capacity, in embodiment 3, the highest actual specific capacity that can reach 135mAh/g, close to the 90% of materials theory capacity (150mAh/g).This also illustrates that ultrasonic-microwave method fundamentally improves the efficiency of the lithium ion deintercalation of positive electrode, is conducive to giving full play to of this material property.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the preparation method of an anode material for lithium-ion batteries, it is characterised in that comprise the following steps:
(1) being dissolved in deionized water by the ferrous sulfate heptahydrate of certain mass ratio and citric acid, stirring is lower adds appropriate dehydrated alcohol, obtains mixture vacuum filtration precipitating out solid, vacuum drying, the ferrous sulfate heptahydrate after being refined;
(2) under inert gas atmosphere, in tetraethylene glycol (TEG) medium, add the ferrous sulfate heptahydrate after the refinement prepared in appropriate step (1), lithium fluoride and dodecylbenzene sodium sulfonate, carry out ultrasonic-microwave heating;
(3) the uniform mixture after step (2) having been processed moves in high-temperature high-pressure reaction kettle, and completes seal operation under inert gas atmosphere, and high-temperature high-pressure reaction kettle is heated;
(4) when high-temperature high-pressure reaction kettle is cooled to room temperature, wherein mixture is taken out, centrifugal, and wash with dichloromethane, last vacuum drying, obtain anode material for lithium-ion batteries.
2. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterised in that the mass ratio of step (1) described ferrous sulfate heptahydrate and citric acid is 10:1.
3. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterized in that, ferrous sulfate heptahydrate and the mol ratio of lithium fluoride after step (2) described refinement are 1:1.15, and described dodecylbenzene sodium sulfonate mass fraction is 0.2～1%.
4. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterized in that, the program of the described ultrasonic-microwave heating of step (2) is set to: exploration type brute force sonication stage time 2～3s, the ultrasonic 1s that is spaced apart, and total ultrasonic time is set to 2～3h; Microwave heating power setting is 50～100w, and temperature is set to 90 DEG C, and set of time is 2～3h.
5. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterized in that, the program of step (3) described heating is set to: is raised to 230～280 DEG C with the heating rate of 1 DEG C/min, and keeps 2～5d at such a temperature.
6. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterised in that the described vacuum drying temperature of step (1) is 35～40 DEG C.
7. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterised in that the described tetraethylene glycol (TEG) medium of step (2) is analytical pure tetraethylene glycol (TEG).
8. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterised in that step (2) and the noble gas described in step (3) are nitrogen.
9. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, it is characterised in that the described vacuum drying temperature of step (4) is 80 DEG C, and the time is 4h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935072A (en) * | 2010-08-26 | 2011-01-05 | 中国科学院化学研究所 | Ferrous lithium sulphate fluoride as well as preparation method and application thereof |
| CN103420411A (en) * | 2013-07-11 | 2013-12-04 | 南京航空航天大学 | Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935072A (en) * | 2010-08-26 | 2011-01-05 | 中国科学院化学研究所 | Ferrous lithium sulphate fluoride as well as preparation method and application thereof |
| CN103420411A (en) * | 2013-07-11 | 2013-12-04 | 南京航空航天大学 | Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles |
Non-Patent Citations (1)
| Title |
|---|
| SHI-LIU YANG ET AL.: "Triethylene Glycol Assisted Synthesis of Pure Tavorite LiFeSO4F Cathode Material for Li-Ion Battery", 《JOURNAL OF THE ELECTROCHEMICAL SOCIET》 * |
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