CN105355859B - A kind of lithium ion battery magnesium, the preparation method of barium doped lithium iron phosphate anode material - Google Patents
A kind of lithium ion battery magnesium, the preparation method of barium doped lithium iron phosphate anode material Download PDFInfo
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- CN105355859B CN105355859B CN201510966624.3A CN201510966624A CN105355859B CN 105355859 B CN105355859 B CN 105355859B CN 201510966624 A CN201510966624 A CN 201510966624A CN 105355859 B CN105355859 B CN 105355859B
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- magnesium
- barium
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- iron phosphate
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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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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- 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
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Abstract
The invention discloses a kind of lithium ion battery magnesium, barium doped lithium iron phosphate anode material and preparation method thereof：By lithium hydroxide, ammonium dihydrogen phosphate, barium carbonate, ferrous oxalate, dysprosia by ball milling after mixing, a nanometer presoma is obtained；Propylene magnesium alkoxide and cosolvent toluene are mixed the magnesium salts colloidal sol to be formed, magnesium salts Sol-gel Coated liquid is obtained, above-mentioned precursor powder is added in surrounding phase ethyl ketone and mixed, add above-mentioned magnesium salts Sol-gel Coated liquid, ball mill；Sintered after drying, obtain magnesium-doped, barium lithium iron phosphate positive material.Lithium ion battery prepared by the present invention lithium iron phosphate positive material for mixing magnesium, barium, while magnesium and barium is doped with to be modified, also being especially added with Dy is modified it, using specific doping, cladding and sintering process, so that the composite is when for lithium ion battery, with higher energy density and good cyclical stability so that lithium ion battery has high specific capacity and longer service life.
Description
Technical field
Mixed the present invention relates to a kind of preparation method of cell positive material, more particularly to a kind of lithium ion battery magnesium, barium
The preparation method of miscellaneous lithium iron phosphate positive material.
Background technology
Battery is the power source of numerous electronic and electrical equipments.Traffic, communication and the fast development of electronic information technology, it is electronic
The deep popularization in people live such as automobile, mobile phone and notebook computer, has all greatly promoted entering for battery technology
Step, so novel battery product emerges in an endless stream.
Lithium ion battery because its have the advantages that capacity height, light weight, small volume and turn into logical, communication and electronic information skill
The available optimal power supply in the fields such as art.LiFePO4 LiFePO4Because its is nontoxic, environmentally friendly, safe, raw material come
Source is abundant, specific capacity height, stable cycle performance, cheap, and the steady electric discharge of the theoretical capacity 3.5V with 170mAh/g is flat
Platform, LiFePO 4 material has high energy density, cheap price, excellent security, is particularly suitable for use in electrokinetic cell.But
Its resistivity is larger.
Due to LiFePO4, under normal temperature, LiFePO4Dynamics it is bad, high rate performance extreme difference, researchers both domestic and external
Used the methods such as cladding, doping, nanosizing improve high rate performance, basic idea be exactly improve electrical conductivity and shorten from
Son, electric transmission path.And the doping of iron position can improve LiFePO4Rate charge-discharge performance, improve cycle performance.Doping gold
Belong to ion to improve its bulk electron electrical conductivity.Poorly conductive is to influence the biggest factor of LiFePO4 application, can by doping
Electrical conductivity is improved, high-rate charge-discharge capability is also improved, the effect of capacity attenuation is inhibited to a certain extent.Doping
Approach can improve, improve lithium ion anode material performance, be a kind of generally acknowledged feasible mode.
The content of the invention
It is an object of the invention to provide the preparation side of a kind of lithium ion battery magnesium, barium doped lithium iron phosphate anode material
Method, the positive electrode prepared using this method, with good cyclical stability and high-rate charge-discharge capability.
To achieve these goals, the present invention is provided a kind of lithium ion battery magnesium, barium doped lithium iron phosphate anode material
The preparation method of material, comprises the following steps：
Step 1, prepare and mix barium LiFePO4 precursor
By lithium source, ammonium dihydrogen phosphate, barium source, ferrous source, dysprosia according to Li: P: Ba: Fe: Dy mol ratio be (0.75-
0.95): 1: (0.05-0.25): (0.99-0.995): after the mixing of (0.005-0.01) ratio, in ethylene glycol medium, rotating speed
600-800r/min high speed ball milling 4-7h, form the slurry that particle diameter is 1-3 microns, by above-mentioned slurries filtration, washing, Ran Houyong
100-110 DEG C of drying obtains a nanometer presoma；
Step 2, magnesium is coated
Propylene magnesium alkoxide and cosolvent are mixed the magnesium salts colloidal sol to be formed, the weight concentration of magnesium salts is 15-25wt% in colloidal sol,
Obtain magnesium salts Sol-gel Coated liquid；
Above-mentioned precursor powder is added in surrounding phase ethyl ketone, the weight ratio of above-mentioned precursor powder and surrounding phase ethyl ketone
Example control is 1: (3-4)；Preferably, then it is stirred, mixing time is preferably 10-15 minutes；
Above-mentioned magnesium salts Sol-gel Coated liquid is added, ball milling obtains coating product, wherein element magnesium and above-mentioned precursor powder
Fe elemental mole ratios are 0.05-0.09: 1；
Step 3, sinter
Above-mentioned cladding product is taken out and dried, the mixture after drying is placed in high temperature furnace, is sintered in blanket of nitrogen, with
5-10 DEG C/min programming rate is heated to 500-600 DEG C, is incubated 6-7h；It is heated to again with 10-15 DEG C/min programming rate
700-800 DEG C, it is incubated 10-12h；600-650 DEG C is down to 15-20 DEG C/min cooling rate again, anneal 5-8h, it is last cold
But, magnesium-doped, barium lithium iron phosphate positive material is obtained.
Wherein, the lithium source is preferably lithium hydroxide.
Wherein, the barium source is preferably barium carbonate.
Wherein, the ferrous source is preferably ferrous oxalate.
Wherein, cosolvent is preferably toluene described in the step 2.
Wherein, ball milling is preferably described in step 2：Implemented in ball mill with rotating speed 100-200r/min, ball milling 30-60
Minute.
Magnesium, the barium doped lithium iron phosphate anode material prepared present invention also offers a kind of above-mentioned any means, especially
Lithium ion battery magnesium, barium doped lithium iron phosphate anode material.
Lithium ion battery prepared by the present invention lithium iron phosphate positive material for mixing magnesium, barium, changes being doped with magnesium and barium
Property while, being also especially added with Dy is modified it, using specific doping, cladding and sintering process so that the composite
When for lithium ion battery, with higher energy density and good cyclical stability so that lithium ion battery has height
Specific capacity and longer service life.
Embodiment
Embodiment one
Barium LiFePO4 precursor is mixed in preparation
It is according to Li: P: Ba: Fe: Dy mol ratio by lithium hydroxide, ammonium dihydrogen phosphate, barium carbonate, ferrous oxalate, dysprosia
After the mixing of 0.95: 1: 0.05: 0.995: 0.005 ratio, in ethylene glycol medium, rotating speed 600r/min high speed ball milling 7h are formed
Particle diameter is 1-3 microns of slurry, by above-mentioned slurries filtration, washing, then obtains a nanometer presoma with 100 DEG C of drying.
Magnesium is coated
Propylene magnesium alkoxide and cosolvent toluene are mixed the magnesium salts colloidal sol to be formed, the weight concentration of magnesium salts is in colloidal sol
15wt%, obtains magnesium salts Sol-gel Coated liquid, and above-mentioned precursor powder is added in surrounding phase ethyl ketone, above-mentioned precursor powder with
The part by weight control of surrounding phase ethyl ketone after stirring is mixed 10 minutes, adds above-mentioned magnesium salts Sol-gel Coated liquid, is put into ball 1: 3
With rotating speed 100r/min in grinding machine, ball milling obtains coating the Fe members of product, wherein element magnesium and above-mentioned precursor powder for 60 minutes
Plain mol ratio is 0.05: 1.
Sintering
Above-mentioned cladding product is taken out and dried, the mixture after drying is placed in high temperature furnace, is sintered in blanket of nitrogen, with
5 DEG C/min programming rate is heated to 500 DEG C, is incubated 6-7h；700 DEG C, insulation are heated to 10 DEG C/min programming rate again
12h；600 DEG C are down to 15 DEG C/min cooling rate again, anneal 8h, finally naturally cools to normal temperature, obtains magnesium-doped, barium
Lithium iron phosphate positive material.
Embodiment two
Barium LiFePO4 precursor is mixed in preparation
It is according to Li: P: Ba: Fe: Dy mol ratio by lithium hydroxide, ammonium dihydrogen phosphate, barium carbonate, ferrous oxalate, dysprosia
After the mixing of 0.75: 1: 0.25: 0.99: 0.01 ratio, in ethylene glycol medium, rotating speed 800r/min high speed ball milling 4h form grain
Footpath is 1-3 microns of slurry, by above-mentioned slurries filtration, washing, then obtains a nanometer presoma with 110 DEG C of drying.
Magnesium is coated
Propylene magnesium alkoxide and cosolvent toluene are mixed the magnesium salts colloidal sol to be formed, the weight concentration of magnesium salts is in colloidal sol
25wt%, obtains magnesium salts Sol-gel Coated liquid, and above-mentioned precursor powder is added in surrounding phase ethyl ketone, above-mentioned precursor powder with
The part by weight control of surrounding phase ethyl ketone after stirring is mixed 15 minutes, adds above-mentioned magnesium salts Sol-gel Coated liquid, is put into ball 1: 4
With rotating speed 200r/min in grinding machine, ball milling obtains coating the Fe members of product, wherein element magnesium and above-mentioned precursor powder for 30 minutes
Plain mol ratio is 0.09: 1.
Sintering
Above-mentioned cladding product is taken out and dried, the mixture after drying is placed in high temperature furnace, is sintered in blanket of nitrogen, with
10 DEG C/min programming rate is heated to 600 DEG C, is incubated 6h；800 DEG C, insulation are heated to 15 DEG C/min programming rate again
10h；600 DEG C are down to 20 DEG C/min cooling rate again, anneal 5h, finally naturally cools to normal temperature, obtains magnesium-doped, barium
Lithium iron phosphate positive material.
Comparative example
By Li2CO3(99.73%), magnesium carbonate (99.5%), BaCO3(99.8%), FeC2O4·2H2O (99.06%),
NH4H2PO4(98%) raw material, is mixed according to the P ratios of 1mol Li: 0.002mol Mg: 0.0003mol Ba: 1mol Fe: 1mol
Afterwards, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn.After 105-120 DEG C of drying, presoma is obtained,
The presoma that drying is obtained is placed in high temperature furnace, and in common purity nitrogen (＞ 99.5%) atmosphere, through 500-750 DEG C, high temperature is forged
Burn 24h.Produce magnesium, the barium-activated lithium iron phosphate cathode material of the present invention
Above-described embodiment one, two and comparative example products therefrom are compressed on nickel screen, it is small in 150 DEG C of vacuum drying 24
When, it is used as working electrode.Reference electrode is lithium metal, and electrolyte is 1mol/l LiPF6EC/DEC/DMC (volume ratio 1: 1:
1).Electric performance test is carried out in the case where test temperature is 25 DEG C, the production of the material and comparative example of the embodiment one and two after tested
Thing is compared, and specific capacity improves 35-45%, and service life improves more than 1.6 times.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (7)
1. a kind of lithium ion battery magnesium, the preparation method of barium doped lithium iron phosphate anode material, comprise the following steps：
Step 1, prepare and mix barium LiFePO4 precursor
By lithium source, ammonium dihydrogen phosphate, barium source, ferrous source, dysprosia according to Li: P: Ba: Fe: Dy mol ratio be (0.75-0.95):
1: (0.05-0.25): (0.99-0.995): after the mixing of (0.005-0.01) ratio, in ethylene glycol medium, rotating speed 600-
800r/min high speed ball milling 4-7h, form the slurry that particle diameter is 1-3 microns, by above-mentioned slurries filtration, washing, then use 100-
110 DEG C of drying obtain a nanometer presoma；
Step 2, magnesium is coated
Propylene magnesium alkoxide and cosolvent are mixed the magnesium salts colloidal sol to be formed, the weight concentration of magnesium salts is 15-25wt% in colloidal sol, is obtained
Magnesium salts Sol-gel Coated liquid；
Above-mentioned nanometer presoma is added in surrounding phase ethyl ketone, the part by weight control of above-mentioned precursor powder and surrounding phase ethyl ketone
System is 1: (3-4), above-mentioned magnesium salts Sol-gel Coated liquid is added, ball milling obtains coating product, wherein element magnesium and above-mentioned precursor powder
The Fe elemental mole ratios of material are 0.05-0.09: 1；
Step 3, sinter
Above-mentioned cladding product is taken out and dried, the mixture after drying is placed in high temperature furnace, is sintered in blanket of nitrogen, with 5-10
DEG C/min programming rate is heated to 500-600 DEG C, is incubated 6-7h；700- is heated to 10-15 DEG C/min programming rate again
800 DEG C, it is incubated 10-12h；600-650 DEG C is down to 15-20 DEG C/min cooling rate again, anneal 5-8h, finally cools down, obtains
To magnesium-doped, barium lithium iron phosphate positive material.
2. according to the method described in claim 1, it is characterised in that the lithium source is lithium hydroxide.
3. according to the method described in claim 1, it is characterised in that the barium source is barium carbonate.
4. according to the method described in claim 1, it is characterised in that the ferrous source is ferrous oxalate.
5. according to the method described in claim 1, it is characterised in that cosolvent described in step 2 is toluene.
6. according to the method described in claim 1, it is characterised in that ball milling is described in step 2：With rotating speed in ball mill
100-200r/min is implemented, ball milling 30-60 minutes.
7. magnesium, barium doped lithium iron phosphate anode material prepared by a kind of method as claimed in claim 1.
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| CN101800315A (en) * | 2010-04-09 | 2010-08-11 | 曲阜毅威能源股份有限公司 | Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof |
| CN102013475A (en) * | 2010-10-22 | 2011-04-13 | 秦波 | Method for preparing porous spherical Li(1-x)MxFe(1-y)Ny(PO4)([3+(alpha-1)x+(beta-2) y]/3)/C material |
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