CN108455550A - A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode - Google Patents
A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode Download PDFInfo
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- CN108455550A CN108455550A CN201810092643.1A CN201810092643A CN108455550A CN 108455550 A CN108455550 A CN 108455550A CN 201810092643 A CN201810092643 A CN 201810092643A CN 108455550 A CN108455550 A CN 108455550A
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- vacuum
- iron phosphate
- lithium
- lithium iron
- phosphate positive
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode is progress batch mixing and activation after dispensing, mixed material is sintered in vacuum drying oven, is quickly cooled down up to high performance lithium iron phosphate positive material；Specific process step：1. by raw material mixed ingredients in proportion, is activated through ball milling, obtain mixed material；2. mixture is placed in vacuum tank, vacuumize, reinject protective gas, so cycle is until oxygen content reaches requirement, constant temperature calcining；3. material is quickly cooled down, classification packaging obtains LiFePO4Positive electrode.Advantage of the present invention:Promote gaseous products to generate under vacuum, reaction temperature and time is reduced, to reduce energy consumption and cost；Inert protective gas dosage is reduced, reduction is ferrous oxidising, enhances product performance；Material is quickly cooled down to reduce temperature fall time, improve material tap density；It avoids carbon content in material from losing, improves lot stability.Suitable for producing lithium iron phosphate positive material.
Description
Technical field
The present invention relates to the manufacturing methods of electrode material, furthermore, it is understood that being related to preparing lithium-ion battery lithium iron phosphate just
The method of pole material.
Background technology
It is well known that anode material for lithium-ion batteries accounts for about 30% or more in battery cost, thus reduce positive electrode at
Originally it is the basic place for reducing power battery price.Meanwhile studies have shown that between positive electrode and electrolyte under the high temperature conditions
Reaction be also to cause the principal element of battery insecurity.Therefore, cheap, electrochemical performance, safety are found
Good positive electrode is the key that lithium-ion-power cell development.
Positive electrode current investigation of materials is more cobalt acid lithium（LiCoO2）, lithium nickelate（LiNiO2）, LiMn2O4（LiMn2O4）With
LiFePO4（LiFePO4）Etc. several.The wherein lithium iron phosphate positive material of olivine shape has it compared with these types of material
Prominent advantage：（1）Theoretical capacity is higher, has 170 mAh/g；（2）Discharge platform with 3.4V（To Li/Li+Electricity
Position）, so that the application range of organic electrolyte is expanded significantly, discharge platform is steady；（3）The good reversibility of electrode reaction, it is negative with carbon
The bulk effect when material mating of pole is good, has extended cycle life；（4）Stable structure, security performance are splendid（O and P is with strong covalent bond jail
Consolidation is closed, and it is difficult analysis oxygen solution to make material）；（5）Chemical stability is very high, and side reaction is few；（6）Without noble element, raw material money
Source is abundant, cheap cheap；（7）High-temperature behavior and thermal stability are substantially better than known other positive electrodes；（8）It is nontoxic, it is true
Positive green material.Above-mentioned advantage makes lithium iron phosphate positive material become the hot spot that countries in the world are competitively researched and developed
One of, it is known as the safe environment protection type lithium ion power battery cathode material of new generation of most future in the world, can be answered extensively
For fields such as new-energy automobile, energy storage device, uninterruptible power supply, electric tools, market prospects are very wide.
LiFePO4The synthetic method of positive electrode mainly has high temperature solid-state method, hydrothermal synthesis method, liquid-phase coprecipitation, molten
Glue-gel method, masterplate method etc., although synthesis LiFePO4Synthetic method it is very much, it is contemplated that technological process is simple and easy to control
The factors such as degree, the characteristics of being easy to industrialization production and production cost, industrialized production selection at present it is most of or high
Warm solid-phase synthesis.But traditional high temperature solid phase synthesis, there are Reaction-diffusion terms speed is slow, reaction temperature is high, and the reaction time is long,
The shortcomings of a large amount of inert atmosphere of need or reduction protection, ferrous ion is oxidizable, carbon coated content loss is big.
Existing scientific and technical personnel have carried out the research for preparing anode material for lithium-ion batteries at present, have applied for a large amount of patents, example
Such as：No. 2012105710559《The preparation method of high-capacity lithium iron phosphate lithium ion battery for automobile anode pole piece》、
No. 201310128555X《A kind of synthetic method of lithium iron phosphate cathode material for lithium ion battery》, No. 2013103380046
《Prepare the hydrothermal synthesis method of the controllable lattice development of lithium iron phosphate positive material》, No. 2016112558304《The compound phosphorus of graphene
Sour iron lithium nanowire positive electrode material and preparation method thereof》, No. 2017101561435《A kind of sulfur doping modified phosphate of high power capacity
The preparation method of iron lithium anode material》Deng.But these patented technologies are not vacuum methodes.
Vacuum method refers to less than 1 atmospheric pressure（101.325kPa）Until ultrahigh vacuum（10-5Pa）Under the conditions of the material that carries out
Material processing building-up process.Vacuum method can effectively facilitate the chemical reaction of gaseous products generation, reduce reaction temperature and time；
It is possible to prevente effectively from oxidation of the oxygen part to material in atmosphere, reduces the generation of impurity thing phase；It is a large amount of that nitrogen, argon gas etc. can be reduced
The dosage of inert protective gas；It can ensure the stability and batch consistency of production.
Invention content
The present invention is intended to provide a kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode, to overcome tradition
High temperature solid phase synthesis prepares LiFePO4Material reaction temperature is high, the time is long, need a large amount of inert atmosphere protections, ferrous iron from
The shortcomings of son is oxidizable, carbon coated content loss is big, tap density is low, lot stability is poor.
The method that inventor provides is to carry out batch mixing and mechanical activation processing after various reaction raw materials are weighed dispensing, will
Mixed material after drying, which is put into be sintered to be quickly cooled down after a certain period of time in vacuum drying oven, can be obtained high performance LiFePO4 just
Pole material；Specific processing step is as follows：
（1）By lithium salts, molysite and microcosmic salt according to Li: Fe: P molar ratio be 0.95~1.05: 1: 1 mixed ingredients, then pass through
Ball milling carries out mechanical activation processing, obtains mixed material；
（2）Mixture is placed in vacuum tank, will first be evacuated in tank, be then injected into protective gas, in material heating, constant temperature
And it remains in stove and vacuumizes and inert atmosphere state in cooling procedure;So cycle is until waiting for that oxygen content is less than 10 × 10-6
（10ppm）Until, then the constant temperature calcining in vacuum drying oven；
（3）After finally the material after constant temperature calcining is quickly cooled down with stove promotion, classification packaging is carried out, LiFePO is obtained4Just
Pole material.
In (1) step of the above method, the ball milling is dry or wet, and Ball-milling Time is controlled in 2~10h；It is wherein wet
Processing need to be dried in material after method ball milling.
The of the above method（2）In step, the injection protective gas is injection nitrogen；The vacuum degree control of the constant temperature calcining
System is in 10~1000Pa, and at 500 DEG C~800 DEG C, roasting time is controlled in 6~16h for temperature control.
In (3) step of the above method, the type of cooling is external air-cooled or water cooling.
The beneficial effects of the invention are as follows:
1. the chemistry for having gaseous products to generate can be promoted anti-by the means of destruction chemical reaction equilibrium under vacuum conditions
It answers, reaction temperature and time is reduced, to reduce energy consumption and production costs；
2. synthesizing iron lithium phosphate battery material under vacuum state can not only be greatly decreased the dosage of inert protective atmosphere, may be used also
To reduce ferrous oxidation in material, enhance product performance；
3. material, which is quickly cooled down, can not only reduce temperature fall time, the tap density of material production can also be improved.
4. synthesizing iron lithium phosphate battery material under vacuum conditions, can be to avoid the damage of carbon content in material synthesis processes
It loses, improves the lot stability of material production.
The present invention is suitable for production lithium iron phosphate positive material.
Description of the drawings
Fig. 1 is the process flow chart of the present invention
Specific implementation mode
The following examples further describe technical scheme of the present invention, but claimed range is not limited to institute
It states.
Embodiment 1
Three kinds of lithium carbonate, diammonium hydrogen phosphate and ferrous oxalate raw materials are matched with Li: Fe: P=0.98: 1: a 1 mole metering than weighing
Material is put into the rate high speed ball milling with 500 r/min in agate jar after preparing, carry out mechanical activation and handle 6h, by material
It is then placed in stainless steel saggar as in vacuum tank, vacuumizes and reinject nitrogen protection atmosphere（Rear oxygen content drops cycle three times
To 1 × 10-6（1ppm）Below）, then the constant temperature calcining 10h under 600 DEG C and 8Pa of vacuum condition, constant temperature is after the completion by vacuum tank
It proposes outside heating furnace, room temperature is quickly cooled to high wind, material taking-up is finally subjected to classification packaging, obtains LiFePO4Anode
Material.
Embodiment 2
Three kinds of lithium hydroxide, diammonium hydrogen phosphate and ferrous oxalate raw materials are matched with Li: Fe: P=1: 1: a 1 mole metering than weighing
Material is put into agate jar the rate high speed ball milling with 600 r/min on planetary ball mill after preparing, it is living to carry out machinery
Change processing 10h, material is then placed in stainless steel saggar as in vacuum tank, vacuumizes and reinjects nitrogen protection atmosphere（It follows
Oxygen content is down to 6 × 10 after ring 3 times-6(6ppm) below）, then the constant temperature calcining 12h under 650 DEG C and 100Pa of vacuum condition,
Vacuum tank is proposed outside heating furnace after the completion of constant temperature, room temperature is quickly cooled to high wind, material taking-up is finally subjected to classification packet
Dress obtains LiFePO4Positive electrode.
Embodiment 3
By three kinds of lithium carbonate, ammonium dihydrogen phosphate and ferrous oxalate raw materials with Li: Fe: P=1.05: 1: 1 mole metering than weighing
It is put into agate jar after dispensing, and deionized water is added in the ratio for being 1: 1.2 according to solid-to-liquid ratio, then with 400 r/min
Rate high speed ball milling, carry out mechanical activation and handle 3h, it is by the slurry after wet ball grinding in dry 6h, the material after drying is right
After be put into stainless steel saggar as in vacuum tank, vacuumize and reinject nitrogen protection atmosphere（Cycle three times be down to by rear oxygen content
10×10-6(10ppm) below）, then the constant temperature calcining 12h under 650 DEG C and 100Pa of vacuum condition, constant temperature is after the completion by vacuum
Tank proposes outside heating furnace, and room temperature is quickly cooled to high wind, and material taking-up is finally carried out classification packaging, obtains LiFePO4Just
Pole material.
Claims (4)
1. a kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode, it is characterised in that this method is will be various anti-
After answering raw material weighing dispensing, batch mixing and mechanical activation processing are carried out, the mixed material after drying is put into vacuum drying oven and is sintered one
It is quickly cooled down after fixing time and can be obtained high performance lithium iron phosphate positive material；Specific processing step is as follows：
（1）By lithium salts, molysite and microcosmic salt according to Li: Fe: P molar ratio be 0.95~1.05: 1: 1 mixed ingredients, then pass through
Ball milling carries out mechanical activation processing, obtains mixed material；
（2）Mixture is placed in vacuum tank, will first be evacuated in tank, be then injected into protective gas, in material heating, constant temperature
And it remains in stove and vacuumizes and inert atmosphere state in cooling procedure；So cycle is until waiting for that oxygen content is less than 10 × 10-6
Until, then the constant temperature calcining in vacuum drying oven；
（3）After finally the material after constant temperature calcining is quickly cooled down with stove promotion, classification packaging is carried out, LiFePO is obtained4Anode
Material.
2. the method as described in claim 1, it is characterised in that the（1）In step, the ball milling is dry or wet, Ball-milling Time
Control is in 2~10h；Processing need to be dried in material wherein after wet ball grinding.
3. the method as described in claim 1, it is characterised in that the（2）In step, the injection protective gas is injection nitrogen；Institute
The vacuum degree control of constant temperature calcining is stated in 10~1000Pa, temperature control at 500 DEG C~800 DEG C, roasting time control 6~
16h。
4. the method as described in claim 1, it is characterised in that the（3）In step, the type of cooling is external air-cooled or water cooling.
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| CN201810092643.1A CN108455550A (en) | 2018-01-31 | 2018-01-31 | A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode |
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| CN201810092643.1A CN108455550A (en) | 2018-01-31 | 2018-01-31 | A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124017A (en) * | 2022-07-26 | 2022-09-30 | 承德锦滦新材料科技有限公司 | Preparation method of lithium vanadium phosphate cathode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789504A (en) * | 2010-03-17 | 2010-07-28 | 中南大学 | Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material |
| CN103413945A (en) * | 2013-08-27 | 2013-11-27 | 昆明理工大学 | Manufacturing method of positive material for lithium ion battery |
-
2018
- 2018-01-31 CN CN201810092643.1A patent/CN108455550A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789504A (en) * | 2010-03-17 | 2010-07-28 | 中南大学 | Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material |
| CN103413945A (en) * | 2013-08-27 | 2013-11-27 | 昆明理工大学 | Manufacturing method of positive material for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 张克宇等: "锂离子电池磷酸铁锂正极材料的研究进展", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124017A (en) * | 2022-07-26 | 2022-09-30 | 承德锦滦新材料科技有限公司 | Preparation method of lithium vanadium phosphate cathode material |
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