CN104009234B - The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium - Google Patents
The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium Download PDFInfo
- Publication number
- CN104009234B CN104009234B CN201410278091.5A CN201410278091A CN104009234B CN 104009234 B CN104009234 B CN 104009234B CN 201410278091 A CN201410278091 A CN 201410278091A CN 104009234 B CN104009234 B CN 104009234B
- Authority
- CN
- China
- Prior art keywords
- microwave
- phosphoric acid
- presoma
- stir
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 3
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 114
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 238000009768 microwave sintering Methods 0.000 claims abstract description 15
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011260 aqueous acid Substances 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 238000009841 combustion method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims description 18
- 229910015645 LiMn Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to one and utilize microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, by Li
2cO
3, Fe
2o
3, phosphoric acid press certain mol proportion metering after, phosphoric acid is made phosphoric acid solution, in phosphoric acid solution, adds citric acid, prepare citric acid, phosphorus aqueous acid; By Li
2cO
3, Fe
2o
3add, stir and obtain paste mixture; Presoma first is obtained after ageing, microwave combustion method; The same manner is with Li
2cO
3, MnCO
3or MnO
2, phosphoric acid is that raw material obtains presoma second, presoma first, second is mixed, adds glucose solution, obtain paste presoma; Positive electrode is obtained finally by microwave sintering.Cell positive material charge/discharge capacity of the present invention and cycle-index better; Battery capacity is high, better performances.Utilize Microwave Treatment accurately to control, technique is simple, pollution-free, is conducive to environmental protection.
Description
Technical field
The present invention relates to a kind of synthetic method of active substance of lithium ion battery anode, particularly relate to one and utilize microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method.
Background technology
Ferric phosphate lithium ion battery is with LiFePO4 (LiFePO
4, being called for short LFP) and material makes the lithium ion battery of anode.First the main advantage of ferric phosphate lithium cell is use safety, the adhesion of phosphate radical chemical bond is stronger than traditional transition metal oxide structural chemistry key, so structure is more stable, and not easily releasing oxygen, LiFePO4 completely solves the security hidden trouble of cobalt acid lithium and LiMn2O4, ferric phosphate lithium cell is the lithium ion battery that the current whole world is uniquely perfectly safe, and stability at high temperature can reach 400-500 DEG C, ensure that the high security of battery inherence; Can not because overcharging, too high, the short circuit of temperature, shock and produce blast or burning; Secondly this battery life overlength, recycle number of times high, at room temperature 1C charge and discharge cycles 2000 times, capability retention more than 80% is more than 2 times of current lithium ion battery, and this battery is not containing any heavy metal and rare metal simultaneously, nontoxic (SGS certification is passed through), pollution-free, meeting European RoHS and specify, is absolute environmental protection battery.
But due to LiFePO
4the restriction of crystal structure own, ionic conductivity is low, and high-rate charge-discharge capability is poor, does not reach the requirement of practical application.And LiMn
0.7fe
0.3pO
4in Mn
3+/2+electricity is at 4.0V ((vsL
+/ Li) near can realize the embedding de-of lithium ion, obtain the capacity of 4.0V platform and improve the energy density of battery, thus causing the great interest of people.
Current preparation LiMn
0.7fe
0.3pO
4the method of material has solid-phase synthesis, coprecipitation etc.But the Solid phase synthesis time is long, and heat utilization rate is low, particle is uneven and easily occur impurity phase.The advantage of coprecipitation is: precursor solution chemical uniformity good (can reach molecular level level), and powder handling performance is good, and course of reaction is easy to control, but its equipment, complex process, the waste water and gas produced is difficult to process, and suitability for industrialized production difficulty is comparatively large, and synthesis cycle is longer.
Microwave heating process be object pass through absorb electromagnetic energy occur from heating process, be a kind of body mode of heating.Because microwave energy is directly by absorption of sample, so sample can evenly be heated rapidly at short notice.Its advantage is energy-conservation, and firing rate is fast, and pollution-free, sample grain refinement, even structure, can accurately control.
Summary of the invention
The object of the invention is: overcome that anode material for lithium-ion batteries complex process in prior art, cost are high, the shortcoming of poor performance, the anode material for lithium-ion batteries LiMn that a kind of reaction time is short, technical process is simple, energy consumption is low, cost is low is provided
0.7fe
0.3pO
4synthetic method.
technical scheme of the present invention:
A kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, comprise the following steps: (1) is by Li
2cO
3, Fe
2o
3, Li, Fe, P in phosphoric acid measure respectively by the mol ratio of 1:0.95 ~ 0.98:0.98 ~ 1.02, in phosphoric acid, add pure water, be mixed with 70 ~ 75wt% phosphoric acid solution; Then in phosphoric acid solution, add the citric acid of its weight 8 ~ 12%, stir, prepare citric acid, phosphorus aqueous acid;
(2) by Li
2cO
3slowly join in described citric acid, phosphorus aqueous acid, stir, then slowly add Fe
2o
3, stir and obtain paste mixture; Then ageing 20 ~ 25 hours;
(3) paste mixture after ageing is placed in non-metallic vessel, puts into microwave oven through microwave combustion method, naturally obtain presoma first after cooling;
(4) by Li
2cO
3, MnCO
3or MnO
2, Li, Mn, P in phosphoric acid measure respectively by the mol ratio of 1:0.95 ~ 0.98:0.98 ~ 1.02, in the phosphoric acid of metering, add pure water, be mixed with the phosphoric acid solution of 75 ~ 80wt%; Then by Li
2cO
3slowly join in phosphoric acid solution, stir; And then slowly add MnO
2, stir and obtain paste mixture; Then ageing 10 ~ 12 hours;
(5) paste mixture after ageing is placed in non-metallic vessel, puts into microwave oven through microwave combustion method, naturally obtain presoma second after cooling;
(6) presoma first, presoma second is measured respectively by the weight ratio of 1:1.95 ~ 2.98, be ground into 150 ~ 200 object particles, be then placed in rubber roll mill grinding 6 ~ 8 hours together, obtain the mixture of presoma first, second;
(7) in the mixture of presoma first, second, add the D/W of its total weight 35 ~ 45%, stir and obtain paste presoma, in described D/W, the content of glucose is 8 ~ 12wt%;
(8) paste presoma is placed in non-metallic vessel, puts into microwave oven through microwave sintering, naturally obtain positive electrode LiMn after cooling
0.7fe
0.3pO
4.
Described Li
2cO
3, Fe
2o
3, MnCO
3or MnO
2for granularity 190 ~ 220 object powdery granule, the mass concentration of phosphoric acid used is 85%.
Microwave combustion method in described step (3) and step (5) utilizes microwave with ramp to 200 ~ 230 DEG C of 3 ~ 8 DEG C per minute, and keep 15 ~ 25 minutes at this temperature;
Described microwave sintering utilizes microwave with ramp to 620 ~ 640 DEG C of 5 ~ 10 DEG C per minute, and keep 15 ~ 25 minutes at this temperature.
Be silicon carbide crucible, graphite crucible, alumina crucible or papery crucible in described non-metallic vessel; Described microwave oven is airtight power is the industrial microwave oven of 20 ~ 25KW.
beneficial effect of the present invention:
(1) early stage of the present invention, raw material mixing adopted solid-liquid combination, added pure water mixing simultaneously, formed paste presoma, can make raw material mixing in early stage evenly, especially metal-doped easier.
(2) the present invention first prepares two kinds of presomas respectively, then grinds after mixing again, and this technique can make the formation of presoma more even, and properties of product are better.
(3) the present invention adopts microwave heating, and microwave energy is directly absorbed by material, so sample can evenly be heated rapidly at short notice, makes material grain refinement, even structure, can accurately control.Microwave combustion method and microwave sintering are carried out in two steps simultaneously, make synthetic reaction more complete.
(4) the present invention's not blanketing with inert gas in microwave sintering process, reduces the requirement of technique to equipment, and equipment simplifies, and is conducive to producing.
(5) the present invention can not produce the pernicious gases such as a large amount of oxynitrides in sintering process, pollution-free, is very beneficial for environmental protection.
(6) anode material for lithium-ion batteries of the present invention effectively improves charge/discharge capacity and the cycle-index of battery; Battery specific energy is higher, and internal resistance is lower, better performances.
Product of the present invention makes positive plate by following technique, and carries out Performance Detection.
First mixed by PVDF and NMP, be configured to the solution of 8%, adopt high speed dispersor mixing, the speed of use revolution 35 revs/min, rotation 1500 revs/min stirs 1 hour, adds conductive carbon material, improves rotational velocity to 2000 rev/min, stirs 1 hour; Add LiMn of the present invention
0.7fe
0.3pO
4, rotation uses the speed of more than 2000 revs/min to stir 3 hours, then adds the viscosity that solvent NMP adjusts solution; The proportion of composing of final solution is as follows: LiMn
0.7fe
0.3pO
4: conductive carbon: PVDF:NMP=100:1:3:70.Above positive solution can use after static 2 hours.Anode sizing agent is coated on equably on the thick aluminium foil of thickness 0.020mm, adopts a large amount of hot air circulation of 80 ~ 150 DEG C to dry.The surface density of coating is 180g/m
2, precision is at 4g/m
2within.To the pressure of 300 tons be adopted to carry out roll-in with superior pole piece, pole piece is compacted, and density reaches 2.7g/cm
3, and cut into the strip pole piece of wide 55mm, long 1350mm.Positive plate and graphite cathode sheet are wound into 26650 batteries.
The discharge capacity first recording battery is 138.6mAh/g, is 132.8mAh/g after 10 circulations; Battery capacity can reach 3100 ~ 3300mAh, and specific energy can reach 480 ~ 504Wh/Kg; About internal resistance 20 milliohm, the continuous discharge within 10C can be carried out.
Accompanying drawing explanation
Fig. 1 is LiMn of the present invention
0.7fe
0.3pO
4the scanning electron microscope (SEM) photograph of 640 DEG C of microwave combustion method.
As can be seen from Figure 1, sample particle is tiny, and distribution of particles is comparatively even, and the largest particles is no more than 5 μm, illustrates that products obtained therefrom particle diameter is tiny and evenly, product quality is better.
Fig. 2 is LiMn of the present invention
0.7fe
0.3pO
4xRD figure.
Can find from the X-ray diffraction spectrum of sample, the corresponding d value of diffraction maximum is consistent with the spectral line in the diffraction card JCPDS74-0375 of standard, shows that prepared sample has olivine crystalline structure, belongs to the space group of rhombic system.
Embodiment
Concrete example illustrates the concrete building-up process of product of the present invention below.
Embodiment one: a kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, comprise the steps:
(1) by Li
2cO
3, Fe
2o
3, Li, Fe, P in phosphoric acid measure respectively by the mol ratio of 1:0.95:0.98, in phosphoric acid, add pure water, be mixed with the phosphoric acid solution of 70 ~ 75wt%; Then in phosphoric acid solution, add the citric acid of its weight 8 ~ 12%, stir, prepare citric acid, phosphorus aqueous acid;
(2) by Li
2cO
3slowly join in described citric acid, phosphorus aqueous acid, stir, then slowly add Fe
2o
3, stir and obtain paste mixture, and ageing 20 ~ 25 hours;
(3) paste mixture after ageing is placed in non-metallic vessel, putting into power is 20 ~ 25KW closed microwave stove, utilize microwave with ramp to 200 ~ 230 DEG C of 3 ~ 8 DEG C per minute, and keep 15 ~ 25 minutes at this temperature, naturally obtain presoma second after cooling;
(4) by Li
2cO
3, MnO
2, Li, Mn, P in phosphoric acid measure respectively by the mol ratio of 1:0.95:0.98, in the phosphoric acid of metering, add pure water, be mixed with the phosphoric acid solution of 75 ~ 80wt%; Then by Li
2cO
3slowly join in phosphoric acid solution, stir; And then slowly add MnO
2, stir and obtain paste mixture, and ageing 10 ~ 12 hours;
(5) paste mixture after ageing is placed in non-metallic vessel, putting into power is 20 ~ 25KW closed microwave stove, utilize microwave with ramp to 200 ~ 230 DEG C of 3 ~ 8 DEG C per minute, and keep 15 ~ 25 minutes at this temperature, naturally obtain presoma second after cooling;
(6) presoma first, presoma second is measured respectively by the weight ratio of 1:1.95, be ground into 150 ~ 200 object particles, be then placed in rubber roll mill grinding 6 ~ 8 hours together, obtain the mixture of presoma first, second;
(7) in the mixture of presoma first, second, add the D/W of its total weight 35 ~ 45%, stir and obtain paste presoma, in described D/W, the content of glucose is 8 ~ 12wt%;
(8) paste presoma is placed in silicon carbide crucible, puts into microwave oven through microwave sintering, naturally obtain positive electrode LiMn after cooling
0.7fe
0.3pO
4; Utilize microwave with ramp to 620 ~ 640 DEG C of 5 ~ 10 DEG C per minute during microwave sintering, and keep 15 ~ 25 minutes at this temperature.
Described Li
2cO
3, Fe
2o
3, MnO
2for granularity 190 ~ 220 object powdered substance, the concentration of phosphoric acid used is 85wt%.
Embodiment two: a kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, comprise the steps:
(1) by Li
2cO
3, Fe
2o
3, Li, Fe, P in phosphoric acid measure respectively by the mol ratio of 1:0.98:1.02, in phosphoric acid, add pure water, be mixed with the phosphoric acid solution of 70%; Then in phosphoric acid solution, add the citric acid of its weight 10%, stir, prepare citric acid, phosphorus aqueous acid;
(2) by Li
2cO
3slowly join in described citric acid, phosphorus aqueous acid, stir, then slowly add Fe
2o
3, stir and obtain paste mixture, ageing 20 hours;
(3) paste mixture after ageing is placed in graphite crucible, puts into the closed microwave stove that power is 20KW, utilize microwave with the ramp to 210 DEG C of 5 DEG C per minute, and keep 20 minutes at this temperature, naturally obtain presoma second after cooling;
(4) by Li
2cO
3, MnO
2, Li, Mn, P in phosphoric acid measure respectively by the mol ratio of 1:0.98:1.02, in the phosphoric acid of metering, add pure water, be mixed with the phosphoric acid solution of 80%; Then by Li
2cO
3slowly join in phosphoric acid solution, stir; And then slowly add MnO
2, stir and obtain paste mixture; Ageing 10 hours;
(5) paste mixture after ageing is placed in graphite crucible, putting into power is 20KW closed microwave stove, utilizes microwave with the ramp to 210 DEG C of 5 DEG C per minute, and keeps 20 minutes at this temperature, naturally obtains presoma second after cooling;
(6) presoma first, presoma second is measured respectively by the weight ratio of 1:2.98, be ground into 150 ~ 200 object particles, be then placed in rubber roll mill grinding 6 ~ 8 hours together, obtain the mixture of presoma first, second;
(7) in the mixture of presoma first, second, add the D/W of its total weight 40%, stir and obtain paste presoma, in described D/W, the mass content of glucose is 8 ~ 12%;
(8) paste presoma is placed in graphite crucible, puts into microwave oven through microwave sintering, naturally obtain positive electrode LiMn after cooling
0.7fe
0.3pO
4; Utilize microwave with the ramp to 630 DEG C of 5 ~ 10 DEG C per minute during microwave sintering, and keep 20 minutes at this temperature.
Described Li
2cO
3, Fe
2o
3, MnO
2granularity be 190 ~ 220 orders, the mass concentration of phosphoric acid is 85%.
Embodiment three: a kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, comprise the steps:
(1) by Li
2cO
3, Fe
2o
3, Li, Fe, P in phosphoric acid measure respectively by the mol ratio of 1:0.96:1, adds the phosphoric acid solution that pure water is mixed with 75% in phosphoric acid; Then in phosphoric acid solution, add the citric acid of its weight 12%, stir, prepare citric acid, phosphorus aqueous acid;
(2) by Li
2cO
3slowly join in described citric acid, phosphorus aqueous acid, stir, then slowly add Fe
2o
3, stir and obtain paste mixture, ageing 25 hours;
(3) paste mixture after ageing is placed in non-metallic vessel, putting into power is 25KW closed microwave stove, utilizes microwave with the ramp to 230 DEG C of 8 DEG C per minute, and keeps 15 minutes at this temperature, naturally obtains presoma second after cooling;
(4) by Li
2cO
3, MnO
2, Li, Mn, P in phosphoric acid measure respectively by the mol ratio of 1:0.96:1, in the phosphoric acid of metering, add pure water, be mixed with the phosphoric acid solution of 80%; Then by Li
2cO
3slowly join in phosphoric acid solution, stir; And then slowly add MnO
2, stir and obtain paste mixture, ageing 12 hours;
(5) paste mixture after ageing is placed in non-metallic vessel, putting into power is 25KW closed microwave stove, utilizes microwave with the ramp to 230 DEG C of 8 DEG C per minute, and keeps 15 minutes at this temperature, naturally obtains presoma second after cooling;
(6) presoma first, presoma second is measured respectively by the weight ratio of 1:2.5, be ground into 150 ~ 200 object particles, be then placed in rubber roll mill grinding 6 ~ 8 hours together, obtain the mixture of presoma first, second;
(7) in the mixture of presoma first, second, add the D/W of its total weight 45%, stir and obtain paste presoma, in described D/W, the mass content of glucose is 12%;
(8) paste presoma is placed in silicon carbide crucible, puts into microwave oven through microwave sintering, naturally obtain positive electrode LiMn after cooling
0.7fe
0.3pO
4; Described microwave sintering utilizes microwave with the ramp to 640 DEG C of 10 DEG C per minute, and keep 15 minutes at this temperature.
Embodiment four: a kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, comprise the steps:
(1) by Li
2cO
3, Fe
2o
3, Li, Fe, P in phosphoric acid measure respectively by the mol ratio of 1:0.97:1.01, in phosphoric acid, add pure water, be mixed with the phosphoric acid solution of 72%; Then in phosphoric acid solution, add the citric acid of its weight 10%, stir, prepare citric acid, phosphorus aqueous acid;
(2) by Li
2cO
3slowly join in described citric acid, phosphorus aqueous acid, stir, then slowly add Fe
2o
3, stir and obtain paste mixture, ageing 22 hours;
(3) paste mixture after ageing is placed in graphite crucible, putting into power is 22KW closed microwave stove, utilizes microwave with the ramp to 220 DEG C of 5 DEG C per minute, and keeps 20 minutes at this temperature, naturally obtains presoma second after cooling;
(4) by Li
2cO
3, MnO
2, Li, Mn, P in phosphoric acid measure respectively by the mol ratio of 1:0.97:1.01, in the phosphoric acid of metering, add pure water, be mixed with the phosphoric acid solution of 78%; Then by Li
2cO
3slowly join in phosphoric acid solution, stir; And then slowly add MnO
2, stir and obtain paste mixture; Ageing 10 hours;
(5) paste mixture after ageing is placed in non-metallic vessel, puts into the closed microwave stove that power is 24KW, utilize microwave with the ramp to 220 DEG C of 6 DEG C per minute, and keep 20 minutes at this temperature, naturally obtain presoma second after cooling;
(6) presoma first, presoma second is measured respectively by the weight ratio of 1:2.25, be ground into 150 ~ 200 object particles, be then placed in rubber roll mill grinding 6 ~ 8 hours together, obtain the mixture of presoma first, second;
(7) in the mixture of presoma first, second, add the D/W of its total weight 38%, stir and obtain paste presoma, in described D/W, the mass content of glucose is 10%;
(8) paste presoma is placed in non-metallic vessel glass pot, puts into microwave oven through microwave sintering, naturally obtain positive electrode LiMn after cooling
0.7fe
0.3pO
4.Described microwave sintering utilizes microwave with the ramp to 630 DEG C of 8 DEG C per minute, and keep 20 minutes at this temperature.
Embodiment five: a kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, substantially identical with embodiment one, difference is: use MnCO
3replace MnO
2.
Embodiment six: a kind of microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, substantially identical with embodiment two, difference is: use MnCO
3replace MnO
2.
Claims (5)
1. a microwave method synthesis of anode material of lithium-ion battery LiMn
0.7fe
0.3pO
4method, it is characterized in that:
(1) by Li
2cO
3, Fe
2o
3, Li, Fe, P in phosphoric acid measure respectively by the mol ratio of 1:0.95 ~ 0.98:0.98 ~ 1.02, in phosphoric acid, add pure water, be mixed with 70 ~ 75wt% phosphoric acid solution; Then in phosphoric acid solution, add the citric acid of its weight 8 ~ 12%, stir, prepare citric acid, phosphorus aqueous acid;
(2) by Li
2cO
3slowly join in described citric acid, phosphorus aqueous acid, stir, then slowly add Fe
2o
3, stir and obtain paste mixture; Then ageing 20 ~ 25 hours;
(3) paste mixture after ageing is placed in non-metallic vessel, puts into microwave oven through microwave combustion method, naturally obtain presoma first after cooling;
(4) by Li
2cO
3, MnCO
3or MnO
2, Li, Mn, P in phosphoric acid measure respectively by the mol ratio of 1:0.95 ~ 0.98:0.98 ~ 1.02, in the phosphoric acid of metering, add pure water, be mixed with the phosphoric acid solution of 75 ~ 80wt%; Then by Li
2cO
3slowly join in phosphoric acid solution, stir; And then slowly add MnO
2, stir and obtain paste mixture; Then ageing 10 ~ 12 hours;
(5) paste mixture after ageing is placed in non-metallic vessel, puts into microwave oven through microwave combustion method, naturally obtain presoma second after cooling;
(6) presoma first, presoma second is measured respectively by the weight ratio of 1:1.95 ~ 2.98, be ground into 150 ~ 200 object particles, be then placed in rubber roll mill grinding 6 ~ 8 hours together, obtain the mixture of presoma first, second;
(7) in the mixture of presoma first, second, add the D/W of its total weight 35 ~ 45%, stir and obtain paste presoma, in described D/W, the content of glucose is 8 ~ 12wt%;
(8) paste presoma is placed in non-metallic vessel, puts into microwave oven through microwave sintering, naturally obtain positive electrode LiMn after cooling
0.7fe
0.3pO
4.
2. cell positive material LiMn according to claim 1
0.7fe
0.3pO
4method, it is characterized in that: described Li
2cO
3, Fe
2o
3, MnCO
3or MnO
2for granularity 190 ~ 220 object powdery granule, the mass concentration of phosphoric acid used is 85%.
3. cell positive material LiMn according to claim 1 and 2
0.7fe
0.3pO
4method, it is characterized in that: the microwave combustion method in described step (3) and step (5) utilizes microwave with ramp to 200 ~ 230 DEG C of 3 ~ 8 DEG C per minute, and keep 15 ~ 25 minutes at this temperature.
4. cell positive material LiMn according to claim 3
0.7fe
0.3pO
4method, it is characterized in that: described microwave sintering utilizes microwave with ramp to 620 ~ 640 DEG C of 5 ~ 10 DEG C per minute, and keep 15 ~ 25 minutes at this temperature.
5. cell positive material LiMn according to claim 4
0.7fe
0.3pO
4method, it is characterized in that: for silicon carbide crucible, graphite crucible, alumina crucible or papery crucible in described non-metallic vessel; Described microwave oven is airtight power is the industrial microwave oven of 20 ~ 25KW.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410278091.5A CN104009234B (en) | 2014-06-20 | 2014-06-20 | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410278091.5A CN104009234B (en) | 2014-06-20 | 2014-06-20 | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104009234A CN104009234A (en) | 2014-08-27 |
| CN104009234B true CN104009234B (en) | 2016-04-06 |
Family
ID=51369804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410278091.5A Active CN104009234B (en) | 2014-06-20 | 2014-06-20 | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104009234B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953108A (en) * | 2015-05-22 | 2015-09-30 | 郑州德朗能微波技术有限公司 | Method for synthesizing lithium ion battery positive electrode material Li(1/4)Na(3/4)/4MnO2 by microwave method |
| CN105236379A (en) * | 2015-10-08 | 2016-01-13 | 绍兴文理学院 | Laboratory preparation method of porous positive material for high-capacity lithium batteries |
| CN106698382A (en) * | 2015-11-12 | 2017-05-24 | 宁夏际华环境安全科技有限公司 | Production technology of lithium iron phosphate |
| CN107742713A (en) * | 2017-10-27 | 2018-02-27 | 天津先众新能源科技股份有限公司 | A kind of synthetic method of graphene/lithium ferric manganese phosphate material |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN116598466B (en) * | 2023-06-20 | 2024-02-23 | 河北九丛科技有限公司 | Preparation method of metal oxide uniformly doped battery-level lithium manganese iron phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102810664A (en) * | 2011-05-30 | 2012-12-05 | 中国科学院宁波材料技术与工程研究所 | Preparation method of monodisperse nanometer olivine type manganese-based phosphate positive-pole material and lithium-ion secondary battery thereof |
| CN103515599A (en) * | 2013-09-29 | 2014-01-15 | 天津大学 | Preparation method for manganese-lithium phosphate and carbon nano tube nanocomposite |
| EP2892091A1 (en) * | 2012-08-28 | 2015-07-08 | Advanced Lithium Electrochemistry Co., Ltd. | Method of producing battery composite material and its precursor |
-
2014
- 2014-06-20 CN CN201410278091.5A patent/CN104009234B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102810664A (en) * | 2011-05-30 | 2012-12-05 | 中国科学院宁波材料技术与工程研究所 | Preparation method of monodisperse nanometer olivine type manganese-based phosphate positive-pole material and lithium-ion secondary battery thereof |
| EP2892091A1 (en) * | 2012-08-28 | 2015-07-08 | Advanced Lithium Electrochemistry Co., Ltd. | Method of producing battery composite material and its precursor |
| CN103515599A (en) * | 2013-09-29 | 2014-01-15 | 天津大学 | Preparation method for manganese-lithium phosphate and carbon nano tube nanocomposite |
Non-Patent Citations (1)
| Title |
|---|
| 掺锰磷酸铁锂的制备及电化学特性研究;张静等;《福建师范大学学报（自然科学版）》;20130630;第29卷(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104009234A (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103109399B (en) | A kind of containing lithium salts-graphene composite material and preparation method thereof | |
| CN104009234B (en) | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium | |
| CN102009970B (en) | Method for preparing high-density lithium ferric phosphate | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN101820062B (en) | Multi-solvent preparation method of lithium iron phosphate | |
| CN102275887A (en) | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof | |
| CN101591012B (en) | Preparation method of lithium iron phosphate as cathode material of lithium ion battery | |
| CN106058307A (en) | Method of preparing lithium ion battery cathode material lithium iron phosphate with lithium iron phosphate waste material | |
| CN102306772A (en) | Method for preparing fluorine sodium ferrous phosphate positive electrode material of mixed ion battery | |
| Ting et al. | Effect of Mn-doping on performance of Li3V2 (PO4) 3/C cathode material for lithium ion batteries | |
| CN102034971A (en) | Lithium-ion battery lithium iron phosphate/polypyrrole pyridine composite anode material and preparation method thereof | |
| CN102903918B (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN101794881A (en) | Method for preparing anode material of lithium ion batteries by one-step microwave sintering | |
| CN102208624A (en) | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method | |
| CN102070187B (en) | Method for preparing spinel lithium titanate serving as negative material of lithium ion battery | |
| CN103887496A (en) | Preparation method of high-performance lithium ion battery positive electrode material LiMBO3@C composite material | |
| CN103199248B (en) | The preparation method of the coated niobium doped iron lithium phosphate of carbon-cobalt acid lithium composite positive pole | |
| CN108110242A (en) | A kind of preparation method of lithium ion battery nickel manganese cobalt composite material | |
| CN104022284B (en) | There is the preparation method of lithium ion battery anode material lithium iron phosphate of ion, electronics hybrid conductive network configuration | |
| CN103693632A (en) | Preparation method of lithium vanadyl phosphate positive material for lithium ion battery | |
| CN105006548A (en) | Method for synthesizing sodium-ion battery positive-electrode material NaFePO4 through microwave method | |
| CN108288698A (en) | A kind of preparation method of lithium iron phosphate positive material | |
| CN106505197B (en) | A method of preparing vanadium phosphate cathode material | |
| CN102983333A (en) | Novel preparation method of lithium vanadium phosphate/carbon composite material for positive pole of lithium ion battery | |
| CN103326021B (en) | The preparation method of lithium iron phosphate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180503 Address after: 277699 Jin Yuan 2, Jining 4, 2 East Road, No. 15 East Road, East Road, Weishan County, Shandong. Patentee after: Shandong DeLong energy Amperex Technology Limited Address before: 450001 14, 13 building, 30 Chemical Road, Zhengzhou high tech Development Zone, Henan Patentee before: Liu Xinbao |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 277600 Building 1, high tech Industrial Park, 36 Dongfeng East Road, Weishan Economic Development Zone, Jining City, Shandong Province Patentee after: Shandong paizhi New Energy Technology Co.,Ltd. Address before: 277699 Jin Yuan 2, Jining 4, 2 East Road, No. 15 East Road, East Road, Weishan County, Shandong. Patentee before: SHANDONG DELANGNENG NEW ENERGY TECHNOLOGY CO.,LTD. |