CN107968195A - Lithium-rich cathode material coated by lithium iron phosphate and preparation method thereof - Google Patents
Lithium-rich cathode material coated by lithium iron phosphate and preparation method thereof Download PDFInfo
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- CN107968195A CN107968195A CN201711175854.3A CN201711175854A CN107968195A CN 107968195 A CN107968195 A CN 107968195A CN 201711175854 A CN201711175854 A CN 201711175854A CN 107968195 A CN107968195 A CN 107968195A
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- lithium
- rich
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- anode material
- lifepo4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 4
- 239000010406 cathode material Substances 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910008514 Li1.2Mn0.54Ni0.13Co0.13O2 Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000005253 cladding Methods 0.000 claims description 27
- 239000010405 anode material Substances 0.000 claims description 24
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910018371 Mn(COOCH3)2 Inorganic materials 0.000 claims description 2
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 229910006525 α-NaFeO2 Inorganic materials 0.000 claims description 2
- 229910006596 α−NaFeO2 Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 229910021311 NaFeO2 Inorganic materials 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000009466 transformation Effects 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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Abstract
The invention discloses a lithium-rich cathode material coated by lithium iron phosphate and a preparation method thereof, belonging to the technical field of lithium ion batteries, and the material comprises a lithium-rich material and lithium iron phosphate coated on the surface of the lithium-rich material, wherein the chemical formula of the lithium-rich material is L iFePO4‑Li1.2Mn0.54Ni0.13Co0.13O2The structure is layered α -NaFeO2Structure, layered space group is Rm, wherein the mass percent of the lithium iron phosphate is 3-7%, the invention coats crystalline L iFePO on the surface of the lithium-rich anode4The surface structure stability of the material is improved, and meanwhile, additional discharge capacity can be provided (L iFePO)4Is electrochemically active) the first coulombic efficiency of the coated sample can reach 91.9%, and the specific discharge capacity under the current of 0.1C can reach 295 mAh/g. The multiplying power performance of the coated sample is greatly improved, the discharge capacity at the multiplying power of 5C can reach 201.8mAh/g, 183.8mAh/g is still obtained after 50 cycles, and the discharge capacity is far higher than that of the uncoated sample. The preparation method is simple, the surface structure is enhanced, the discharge capacity is high, and the rate capability and the cycle performance are better.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically a kind of LiFePO4 cladding lithium-rich anode material and its
Preparation method.
Background technology
It is mobile whole in recent years since the high speed development of the Internet, applications and people give more sustained attention global environmental problems
End (particularly smart mobile phone) and electric automobile field increase the demand of high energy density cells, big specific capacity and high workload electricity
The positive electrode of pressure receives increasing concern.Commercial positive electrode LiCoO at present2、LiMn2O4、LiFePO4And ternary
LiMnxCoyNi1-x-yO2Specific discharge capacity be below 200mAh/g.In contrast, rich lithium material xLi2MnO3·(1-x)LiMO2
The specific discharge capacity of 250mAh/g, while its high operating voltage, low production cost and advantages of environment protection are had more than,
In the case where continuing to develop in recent years, it is expected to as the anode material for lithium-ion batteries of a new generation.
Although lithium-rich anode material has the advantage of high reversible capacity and low cost, there is also the effect of coulomb first
The shortcomings of rate is low and cycle life is insufficient, seriously constrains the application of lithium-rich anode material in practice.Lithium-rich anode material
High power capacity derives from Li under high voltages during initial charge2MnO3Activation process, that is, Li in lattice2O's is irreversible
Abjection is at the same time with the generation of Lacking oxygen.Because this decomposition of irreversible activation process and electrolyte under high voltages,
It result in the low coulombic efficiency first of lithium-rich anode material.Lithium-rich anode material is from layer structure to spinelle in charge and discharge process
The transformation of structure is the main reason for causing lithium-rich anode material poor circulation.
In order to further improve its coulombic efficiency and cycle performance first, we are prepared for LiFePO with simple precipitation method4
The Li of cladding1.2Mn0.54Ni0.13Co0.13O2(LMNCO) lithium-rich anode material, back to back roasting process are used for strengthening interface
Structural stability.Compared to uncoated material, the lithium-rich anode material after cladding has specific discharge capacity, the high head of bigger
Cycle performance under secondary coulombic efficiency and good cycle performance, particularly high magnification.
The content of the invention
It is an object of the invention to overcome defect existing in the prior art, there is provided a kind of lithium-rich anode of LiFePO4 cladding
Material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of lithium-rich anode material of LiFePO4 cladding, including rich lithium material and the phosphoric acid for being coated on rich lithium material surface
Iron lithium, its chemical formula are LiFePO4-Li1.2Mn0.54Ni0.13Co0.13O2, structure is stratiform α-NaFeO2Structure, the space of stratiform
Group beWherein the mass percent of LiFePO4 is 3-7%.
It is another object of the present invention to provide a kind of preparation method of the lithium-rich anode material of LiFePO4 cladding, bag
Include following steps：
(1) Li is prepared1.2Mn0.54Ni0.13Co0.13O2：According to Li:Mn:Ni:The molar ratio of Co is 1.32:0.54:0.13:
0.13 weighs LiCOOCH3·2H2O、Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH3)2·4H2O, be dissolved in from
In sub- water, mixing salt solution is made into；According to citric acid：Metal ion=3:1, aqueous citric acid solution is added to mixing salt solution
In, 80 DEG C are heated to, magnetic stirring 4h, forms pink clear gel；Gel is moved into drying in air dry oven, box
Pre-burning 5h under 480 DEG C of air atmospheres in stove, takes out grinding, then moves into 900 DEG C of calcining 12h in Muffle furnace, is made
Li1.2Mn0.54Ni0.13Co0.13O2Powder；
(2) lithium-rich anode material of LiFePO4 cladding is prepared：According to molar ratio Li:Fe is 1:1 weighs respectively
LiCOOCH3·2H2O and FeSO4·7H2O, is dissolved in deionized water, according to molar ratio Li:P=1:1, by NH4H2PO4Aqueous solution
It is slowly dropped into wherein and is stirred continuously, is subsequently added into the Li of step (1) preparation1.2Mn0.54Ni0.13Co0.13O2Powder, heating sealing
Magnetic stirs, and is washed after standing 12h, is slightly ground after dry, moves into tube furnace the 300-500 DEG C of roasting 3- under protective atmosphere
5h, is made the lithium-rich anode material of LiFePO4 cladding.
Further scheme, step (1) drying temperature are 80 DEG C, drying time 12h.
Further scheme, the heating rates of 900 DEG C of calcinings are 4 DEG C/min in the step (1).
Further scheme, the middle heating sealing magnetic stirring of the step (2) are：60-100 DEG C is heated to, magnetic mixing speed is
80-180r/min, preferably mixing speed 160r/min, magnetic mixing time are 3-5h, preferably mixing time 4h.
Further scheme, the middle washing of the step (2) are to use deionized water and absolute ethyl alcohol centrifugal elutriation three times successively.
Further scheme, protective atmosphere is high-purity argon gas in the step (2).
Beneficial effects of the present invention：
1st, the present invention passes through the LiFePO in lithium-rich anode surface cladding crystalline state4, improve material surface texture stablize
Property, while extra discharge capacity (LiFePO can be provided4It is electro-chemical activity) effect of coulomb first of sample after cladding
Rate can reach 91.9%, and specific discharge capacity is up to 295mAh/g under 0.1C (1C=300mA/g) electric current.After particularly coating
The high rate performance of sample is greatly improved, and 5C multiplying powers discharge capacity can reach 201.8mAh/g, after 50 circulations still
So there is 183.8mAh/g, significantly larger than uncoated sample.
2nd, preparation method of the present invention is simple, enhances surface texture and (reduces and contacted with the direct of electrolyte, suppress the molten of Mn
Solution), discharge capacity is high, and high rate performance and cycle performance are more preferably.
Brief description of the drawings
Fig. 1 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) XRD spectrum.
Fig. 2 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) SEM figures；Wherein：(a) (b) LMNCO, (c) (d) LFP-400, (e) (f) LFP-500.
Fig. 3 is (a) LMNCO, (b) LFP-400, the HRTEM images of (c) LFP-500 samples, and the EDS of (d) LFP-400 schemes
Picture.
Fig. 4 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) first charge-discharge curve map.
Fig. 5 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) cyclic curve figure under (a) 1C and (b) 5C electric currents.
Fig. 6 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) high rate performance figure.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) Li is prepared1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Mn:Ni:Co is 1.32:0.54:0.13:0.13 ratio measures LiCOOCH3·2H2O, Mn
(COOCH3)2, Ni (COOCH3)2·4H2O, Co (COOCH3)2·4H2O, is dissolved in 100mL deionized waters, it is molten to obtain salt-mixture
Liquid；Then a certain amount of citric acid (citric acid：Metal ion=3:1 molar ratio) it is dissolved in 50mL deionized waters and stirs evenly；
Aqueous citric acid solution is slowly dropped in mixing salt solution, 80 DEG C, when magnetic stirring 4 is small is heated to, it is transparent solidifying to form pink
Glue, when gel is moved into 80 DEG C of dryings 12 are small in air dry oven, when pre-burning 5 is small under 480 DEG C of air atmospheres in batch-type furnace,
Take out grinding, then move into Muffle furnace 900 DEG C of calcinings 12 it is small when, calcination stage heating rate is 4 DEG C/min, you can is obtained
Li1.2Mn0.54Ni0.13Co0.13O2(LMNCO) powder.
(2) LiFePO is prepared4The Li of cladding1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Fe=1:1,0.0324gLiCOOCH is weighed respectively3·2H2O and 0.0881gFeSO4·7H2O,
It is dissolved in 40mL deionized waters；By 0.0365gNH4H2PO4(Li:P=1:1) it is dissolved in 10mL deionizations, then by ammonium dihydrogen phosphate
Aqueous solution is slowly dropped into wherein and is stirred continuously, and is subsequently added into the LMNCO powder of 1g steps (1) preparation, is heated to 80 DEG C, with
When the speed sealing magnetic stirring 4 of 180r/min is small, stand 12 it is small when after, with deionized water and absolute ethyl alcohol centrifugal elutriation three times,
Slightly ground after drying, when the lower 400 DEG C of roastings 5 of argon gas flox condition are small in immigration tube furnace, gained covering material is labeled as
LFP-400, the amount of cladding is 5wt%, the LiFePO of cladding4It is crystalline state.
Embodiment 2
(1) Li is prepared1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Mn:Ni:Co is 1.32:0.54:0.13:0.13 ratio measures LiCOOCH3·2H2O, Mn
(COOCH3)2, Ni (COOCH3)2·4H2O, Co (COOCH3)2·4H2O, is dissolved in 100mL deionized waters, it is molten to obtain salt-mixture
Liquid；Then a certain amount of citric acid (citric acid：Metal ion=3:1 molar ratio) it is dissolved in 50mL deionized waters and stirs evenly；
Aqueous citric acid solution is slowly dropped in mixing salt solution, 80 DEG C, when magnetic stirring 4 is small is heated to, it is transparent solidifying to form pink
Glue, when gel is moved into 80 DEG C of dryings 12 are small in air dry oven, when pre-burning 5 is small under 480 DEG C of air atmospheres in batch-type furnace,
Take out grinding, then move into Muffle furnace 900 DEG C of calcinings 12 it is small when, calcination stage heating rate is 4 DEG C/min, you can is obtained
Li1.2Mn0.54Ni0.13Co0.13O2(LMNCO) powder.
(2) LiFePO is prepared4The Li of cladding1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Fe=1:1,0.0324gLiCOOCH is weighed respectively3·2H2O and 0.0881gFeSO4·7H2O,
It is dissolved in 40mL deionized waters；By 0.0365gNH4H2PO4(Li:P=1:1) it is dissolved in 10mL deionizations, then by ammonium dihydrogen phosphate
Aqueous solution is slowly dropped into wherein and is stirred continuously, and is subsequently added into the LMNCO powder of 1g steps (1) preparation, is heated to 80 DEG C, with
When the speed sealing magnetic stirring 5 of 160r/min is small, stand 12 it is small when after, with deionized water and absolute ethyl alcohol centrifugal elutriation three times,
Slightly ground after drying, when the lower 500 DEG C of roastings 5 of argon gas flox condition are small in immigration tube furnace, gained covering material is labeled as
LFP-500, the amount of cladding is 5wt%, the LiFePO of cladding4It is crystalline state.
XRD, SEM of LFP-400 made from pure rich lithium material LMNCO, embodiment 1, LFP-500 made from embodiment 2
With TEM results difference as shown in Figure 1, 2, 3.Electrochemical property test is carried out using 2032 button cells：According to active material：Charcoal
It is black：Poly- (vinylidene fluoride) is 75:15:10 mass ratio is dissolved in N methyl pyrrolidones, is uniformly applied on aluminium foil, 120 DEG C
Positive plate is made after dried overnight.Anode is lithium piece, and membrane is Celgard 2400, and electrolyte is dissolved in EC/ for 1M LiPF6
DMC/DEC(1:1:1in wt.%).The assembling process of battery is completed in glove box.The charge-discharge test of battery is in new prestige CT-
Carried out on 3008.First charge-discharge curve, cycle performance and the high rate performance difference of sample are as shown in Figure 4,5, 6.After cladding
The coulombic efficiency first of sample can reach 91.9%, and specific discharge capacity is up under 0.1C (1C=300mA/g) electric current
295mAh/g.The high rate performance of sample is greatly improved after particularly coating, and 5C multiplying powers discharge capacity can reach
201.8mAh/g, still has 183.8mAh/g, significantly larger than uncoated sample after 50 circulations.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make case study on implementation various modifications, and described herein one
As principle be applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation case here
Example, those skilled in the art disclose according to the present invention, and not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (7)
1. a kind of lithium-rich anode material of LiFePO4 cladding, it is characterised in that including rich lithium material and be coated on rich lithium material
The LiFePO4 on surface, its chemical formula are LiFePO4-Li1.2Mn0.54Ni0.13Co0.13O2, structure is stratiform α-NaFeO2Structure,
The space group of stratiform is RThe mass percent of m, wherein LiFePO4 are 3-7%.
2. the preparation method of the lithium-rich anode material of LiFePO4 as claimed in claim 1 cladding, it is characterised in that including with
Lower step：
（1）Prepare Li1.2Mn0.54Ni0.13Co0.13O2：According to Li:Mn:Ni:The molar ratio of Co is 1.32:0.54:0.13:0.13 claims
Take LiCOOCH3·2H2O、Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH3)2·4H2O, is dissolved in deionized water
In, it is made into mixing salt solution；According to citric acid：Metal ion=3:1, aqueous citric acid solution is added in mixing salt solution, is added
For heat to 80 DEG C, magnetic stirring 4h, forms pink clear gel；Gel is moved into drying in air dry oven, in batch-type furnace
Pre-burning 5h under 480 DEG C of air atmospheres, takes out grinding, then moves into 900 DEG C of calcining 12h in Muffle furnace, is made
Li1.2Mn0.54Ni0.13Co0.13O2Powder；
（2）Prepare the lithium-rich anode material of LiFePO4 cladding：According to molar ratio Li:Fe is 1:1 weighs LiCOOCH respectively3·
2H2O and FeSO4·7 H2O, is dissolved in deionized water, according to molar ratio Li:P=1:1, by NH4H2PO4Aqueous solution is slowly dropped into it
In and be stirred continuously, be subsequently added into step（1）The Li of preparation1.2Mn0.54Ni0.13Co0.13O2Powder, heating sealing magnetic stirring are quiet
Wash after putting 12h, slightly ground after dry, move into tube furnace the 300-500 DEG C of roasting 3-5h under protective atmosphere, phosphoric acid is made
The lithium-rich anode material of iron lithium cladding.
3. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 1, it is characterised in that described
Step（1）Drying temperature is 80 DEG C, drying time 12h.
4. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（1）In 900 DEG C calcining heating rates be 4 DEG C/min.
5. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（2）Middle heating sealing magnetic, which stirs, is：60-100 DEG C is heated to, magnetic mixing speed is 80-180r/min, preferably mixing speed
160r/min, magnetic mixing time are 3-5h, preferably mixing time 4h.
6. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（2）Middle washing is to use deionized water and absolute ethyl alcohol centrifugal elutriation three times successively.
7. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（2）Middle protective atmosphere is high-purity argon gas.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037660A (en) * | 2018-09-04 | 2018-12-18 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of preparation method of composite lithium iron phosphate material |
| CN114242980A (en) * | 2021-12-16 | 2022-03-25 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate composite material, preparation method and application |
| WO2022109886A1 (en) * | 2020-11-25 | 2022-06-02 | 宁德时代新能源科技股份有限公司 | Composite positive electrode material and preparation method therefor, positive electrode plate, secondary battery and battery module comprising same, battery pack, and device |
| CN114725369A (en) * | 2022-02-10 | 2022-07-08 | 中国第一汽车股份有限公司 | High-energy-density positive electrode material, positive electrode plate and lithium ion battery |
| CN116154144A (en) * | 2023-04-24 | 2023-05-23 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, positive electrode plate, battery cell, battery and electric equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035906A (en) * | 2013-01-08 | 2013-04-10 | 南开大学 | Lithium manganese phosphate clad lithium-rich layered oxide cathode material as well as preparation and application thereof |
| CN103280574A (en) * | 2013-05-29 | 2013-09-04 | 上海电力学院 | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material |
| CN103904311A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Surface coating and compounding lithium-rich manganese-based positive electrode material and preparation method of positive electrode material |
| CN105742622A (en) * | 2016-03-27 | 2016-07-06 | 华南理工大学 | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor |
-
2017
- 2017-11-22 CN CN201711175854.3A patent/CN107968195A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904311A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Surface coating and compounding lithium-rich manganese-based positive electrode material and preparation method of positive electrode material |
| CN103035906A (en) * | 2013-01-08 | 2013-04-10 | 南开大学 | Lithium manganese phosphate clad lithium-rich layered oxide cathode material as well as preparation and application thereof |
| CN103280574A (en) * | 2013-05-29 | 2013-09-04 | 上海电力学院 | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material |
| CN105742622A (en) * | 2016-03-27 | 2016-07-06 | 华南理工大学 | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| HE LEI等: "LiFePO4-Coated Li1.2Mn0.54Ni0.13CO0.13O2 as Cathode Materials with High Coulombic Efficiency and Improved Cyclability for Li-Ion Batteries", 《ACTA PHYS. -CHIM. SIN.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037660A (en) * | 2018-09-04 | 2018-12-18 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of preparation method of composite lithium iron phosphate material |
| WO2022109886A1 (en) * | 2020-11-25 | 2022-06-02 | 宁德时代新能源科技股份有限公司 | Composite positive electrode material and preparation method therefor, positive electrode plate, secondary battery and battery module comprising same, battery pack, and device |
| CN116114082A (en) * | 2020-11-25 | 2023-05-12 | 宁德时代新能源科技股份有限公司 | Composite positive electrode material, preparation method thereof, positive electrode plate, secondary battery, battery module comprising secondary battery, battery pack and device |
| US11855277B2 (en) | 2020-11-25 | 2023-12-26 | Contemporary Amperex Technology Co., Limited | Composite positive-electrode material and preparation method thereof, positive-electrode plate, secondary battery, and battery module, battery pack, and apparatus containing such secondary battery |
| CN114242980A (en) * | 2021-12-16 | 2022-03-25 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate composite material, preparation method and application |
| WO2023108961A1 (en) * | 2021-12-16 | 2023-06-22 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate composite material, and preparation method therefor and use thereof |
| CN114242980B (en) * | 2021-12-16 | 2023-10-31 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate composite material, preparation method and application |
| CN114725369A (en) * | 2022-02-10 | 2022-07-08 | 中国第一汽车股份有限公司 | High-energy-density positive electrode material, positive electrode plate and lithium ion battery |
| CN116154144A (en) * | 2023-04-24 | 2023-05-23 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, positive electrode plate, battery cell, battery and electric equipment |
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