CN101330141B - Method for preparing lithium ionic battery anode material spherical LiFePO4 /C - Google Patents
Method for preparing lithium ionic battery anode material spherical LiFePO4 /C Download PDFInfo
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- CN101330141B CN101330141B CN2008101168216A CN200810116821A CN101330141B CN 101330141 B CN101330141 B CN 101330141B CN 2008101168216 A CN2008101168216 A CN 2008101168216A CN 200810116821 A CN200810116821 A CN 200810116821A CN 101330141 B CN101330141 B CN 101330141B
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 11
- 229910052493 LiFePO4 Inorganic materials 0.000 title description 2
- 238000005303 weighing Methods 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 10
- 229930006000 Sucrose Natural products 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000005720 sucrose Substances 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 8
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 8
- 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
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 239000002562 thickening agent Substances 0.000 claims description 18
- 229910010710 LiFePO Inorganic materials 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- -1 phosphate compound Chemical class 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 abstract description 2
- 229910000901 LiFePO4/C Inorganic materials 0.000 abstract 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract 3
- 239000002243 precursor Substances 0.000 abstract 2
- 239000000725 suspension Substances 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002642 lithium compounds Chemical group 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere 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
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
A process for preparing the high-density spherical LiFePO4/C anode material of lithium ion batteries belongs to the technical field of the energy material. The process comprises the following steps: weighing Fe2O3, a phosphate compound and a lithium-source compound by a stoichiometric ratio; slowly adding to one or more aqueous solutions of hexane diacid, polyethylene glycol, polyacrylic acid or polyvinyl alcohol, and adding one or more of conductive carbon black, sucrose and glucose in a certain amount as well as the doping ions, heating, ball-milling and stirring to form an uniform suspension; spray-drying the obtained suspension to obtain the spherical mixed powder precursor; and carrying out the heat treatment of the precursor under the protection of the inert gas to obtain the high-density high-conductivity LiFePO4/C anode material. The prepared LiFePO4/C anode material granule is spherical, has a tap density as high as 1.35-1.45g*cm<-3>, a larger specific surface area and good conductivity, and has high application value in the field of the power-type lithium ion batteries.
Description
Technical field
The present invention relates to a kind of preparation technology of lithium ion battery high-density spherical ferric lithium phosphate positive electrode, belong to the energy and material technical field.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, is widely used in fields such as mobile phone, notebook computer.Yet at present lithium ion battery is still based on low capacity, low battery power, in big capacity, in the not large-scale production as yet of high-power lithium ion battery, make lithium ion battery not be used widely as yet in the motive-power battery field.The popularization and application of motive-power battery need obtain important breakthrough on electrode material.
Positive electrode is the important component part of lithium ion battery.Studying maximum positive electrodes so far is lithium-compound transition metal oxide positive electrode and polyanion type positive electrode, mainly comprises LiCoO
2, LiNiO
2, LiMn
2O
4, LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2, LiFePO
4And Li
3V
2(PO
4)
3Deng.Concerning power-type lithium ion battery, the cost of positive electrode, cycle performance, fail safe are very important.The LiFePO of quadrature olivine structural
4Positive electrode has become new research focus both at home and abroad with its outstanding performance.Primary Study shows, LiFePO
4Positive electrode raw material cheapness; Stability Analysis of Structures, security performance is splendid; Cycle performance and thermal stability obviously are better than other positive electrode; Bulk effect when cooperating with carbon negative pole material during charging is good; Good with most of electrolyte system compatibilities, storge quality is good; Nontoxic.LiFePO
4Positive electrode is expected to become the desirable positive electrode of power-type lithium ion battery because have outstanding advantage aspect cost, cycle performance, the fail safe.
The advantage of LiFePO4 is very outstanding, but also exists some shortcomings, and the one, the intrinsic electronic conductivity that it is extremely low, this has had a strong impact on the large-current electric chemical property of this material; The 2nd, the product bulk density that adopts conventional synthetic method to synthesize is lower, has limited the practical application of this material in high power high energy density lithium ion field of batteries.Current, people are improving LiFePO
4The research aspect of conductivity and bulk density has obtained many progress.The measure of the raising conductivity of taking usually has: granule interior is mixed conductive carbon material or conductive metal particle; Particle surface coated with conductive material with carbon element; The doping of metal ion; Reduce LiFePO
4The size of crystal grain, even the powder particle of synthesis of nano size.The measure of the raising bulk density of taking usually is the powder particle of synthesizing spherical pattern, and the control particle size distribution.
Synthetic LiFePO
4Method have a variety ofly, the source of iron raw material of employing is also varied.Wherein the synthetic method of cheap and simple is a high-temperature solid phase reaction method the most, a kind of method is for after adopting comparatively expensive ferrous oxalate of price or ferrous acetate divalence source of iron raw material and phosphate and lithium salt compound and mixing, and pyroreaction makes under inert gas shielding; Another kind method is for after adopting di-iron trioxide or ferric phosphate ferric iron source raw material and phosphate and lithium salt compound and mixing; add carbon-source cpd or metal iron powder again, pyrocarbon thermal reduction reaction or high temperature iron thermal reduction reaction make under inert gas shielding.Though the high-temperature solid phase reaction method synthesis process is simple, the cost of material height that has can not effectively reduce LiFePO
4Cost; The more important thing is synthetic LiFePO
4Product particle is random pattern, and bulk density is lower.The applicant had once invented " crystallization control " technology, was the synthesizing spherical FePO of raw material elder generation with ferric nitrate or iron chloride
4Presoma is again by pyrocarbon thermal reduction reaction synthesizing spherical LiFePO
4Method, the product particle that this method obtains has higher bulk density for spherical; And by reduce crystallite dimension, granule interior is mixed conductive materials, coated with carbon material and is carried out ion doping, has improved the large-current electric chemical property of material largely.Though this method has solved LiFePO simultaneously
4The problem of material bulk density and conductivity, but preparation technology or more complicated, LiFePO
4The cost of product is still higher.
Summary of the invention
The objective of the invention is to propose a kind of lithium ion battery anode material spherical LiFePO
4The preparation method of/C makes the product particle of its preparation not only spherical in shape, has higher tap density and large-current electric chemical property preferably; And technology is simpler, and synthetic cost is cheaper, thereby further reduces LiFePO
4The cost of material.
Technical scheme of the present invention is as follows:
A kind of anode material for lithium-ion batteries high-density spherical LiFePO
4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion
2O
3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO
4Product quality percentage is 1～5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd;
2) slowly to join mass concentration be in 5%～30% the organic compound aqueous thickener solution, under the heating and ball-milling stirring condition, to make mixed solution form uniform suspension-turbid liquid to the compound that step 1) is taken by weighing;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical powder;
4) with the spherical powder of step 3) gained under inert gas shielding in 700 ℃～900 ℃ following heat treatments 8～20 hours, promptly obtain spherical LiFePO
4/ C product.
The present invention also provides a kind of anode material for lithium-ion batteries high-density spherical Li doped FePO
4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion
2O
3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO
4Product quality percentage is 1～5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd is nitrate or the acetate that M/Li=0.5%～2% takes by weighing doped metal ion M more in molar ratio; A kind of among doped metal ion M=Mg, Mn, Zr, Mo or the Cr;
2) slowly to join mass concentration be in 5%～30% the organic compound aqueous thickener solution to the compound that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical adulterated powder;
4) with the spherical adulterated powder of step 3) gained under inert gas shielding in 700 ℃～900 ℃ following heat treatments 8～20 hours, promptly obtain spherical Li doped FePO
4/ C product.
In the technique scheme, described phosphate compounds is LiH
2PO
4, NH
4H
2PO
4With (NH
4)
2HPO
4In a kind of, Li source compound is CH
3COOLi2H
2O, LiCO
3Or LiOHH
2A kind of among the O, carbon-source cpd is sucrose or glucose; The organic compound thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more.
The present invention adopts the Fe that is dirt cheap
2O
3Be raw material; with P source compound, Li source compound, carbon-source cpd and thickener mixed uniform suspension-turbid liquid; adopt spray-dired method to obtain spherical mixed powder presoma again, the heat treatment presoma is promptly prepared the spherical LiFePO of high density high conductivity under inert gas shielding
4/ C positive electrode.And this method can also realize the even carbon dope of metal ion mixing and spheric granules inside with comparalive ease, further improves the conductivity of material.This method is than " crystallization control " technology, and product has the feature of high density high conductivity equally, but technological process is simpler, and product cost is cheaper; The LiFePO for preparing
4/ C and Li doped FePO
4/ C powder particle is spherical in shape, has higher tap density and large-current electric chemical property preferably simultaneously; Has very big using value in the power-type lithium ion battery field.
Embodiment
A kind of anode material for lithium-ion batteries high-density spherical LiFePO provided by the invention
4The preparation method of/C, its concrete preparation technology is as follows:
1) takes by weighing Fe respectively by stoichiometric proportion
2O
3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO
4Product quality percentage is 1～5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd, phosphate compounds are LiH
2PO
4, NH
4H
2PO
4With (NH
4)
2HPO
4In a kind of, Li source compound is CH
3COOLi2H
2O, LiCO
3Or LiOHH
2A kind of among the O, carbon-source cpd is sucrose or glucose;
2) slowly to join mass concentration be in 5%～30% the organic compound aqueous thickener solution to the compound that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid carries out spray drying, obtains spherical powder;
4) with the spherical powder of step 3) gained under inert gas shielding in 700 ℃～900 ℃ following heat treatments 8～20 hours, promptly obtain spherical LiFePO
4/ C product.
The present invention also provides a kind of anode material for lithium-ion batteries high-density spherical Li doped FePO
4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion
2O
3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO
4Product quality percentage is 1～5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd is nitrate or the acetate that M/Li=0.5%～2% takes by weighing doped metal ion M more in molar ratio; Described phosphate compounds is LiH
2PO
4, NH
4H
2PO
4With (NH
4)
2HPO
4In a kind of, described Li source compound is CH
3COOLi2H
2O, LiCO
3Or LiOHH
2A kind of among the O, carbon-source cpd is sucrose or glucose; A kind of among doped metal ion M=Mg, Mn, Zr, Mo or the Cr;
2) slowly to join mass concentration be in 5%～30% the organic compound aqueous thickener solution to the compound that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid employing pneumatic spray drying, obtain spherical adulterated powder;
4) with the spherical adulterated powder of step 3) gained under inert gas shielding in 700 ℃～900 ℃ following heat treatments 8～20 hours, promptly obtain spherical Li doped FePO
4/ C product.
Introduce embodiments of the invention below:
Embodiment 1. takes by weighing 400g Fe
2O
3, 660.3g (NH
4)
2HPO
4, 185.93g LiCO
3, 39.25g conductive carbon black and 142.6g sucrose, slowly add mass concentration and be in 20% the Polyacrylate thickeners aqueous solution, heating and ball-milling mixes solution, form uniform suspension-turbid liquid, resulting suspension-turbid liquid pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1Mpa, and the control temperature of inlet air is 300 ℃, and outlet is 100 ℃, and outlet air separates emptying through the one-level vortex.Spray drying gained powder promptly obtains spherical LiFePO in 800 ℃ of following heat treatments after 15 hours under inert gas shielding
4/ C product.Recording this product tap density is 1.41gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 151mAh/g.
Embodiment 2. takes by weighing 400g Fe
2O
3, 519.8g LiH
2PO
4, 23.55g conductive carbon black and 150g glucose, slowly add mass concentration and be in 30% the polyethylene glycol aqueous thickener solution, heating and ball-milling mixes solution, form uniform suspension-turbid liquid, resulting suspension-turbid liquid pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1Mpa, and the control temperature of inlet air is 300 ℃, and outlet is 100 ℃, and outlet air separates emptying through the one-level vortex.Spray drying gained powder promptly obtains spherical LiFePO in 700 ℃ of following heat treatments after 20 hours under inert gas shielding
4/ C product.Recording this product tap density is 1.42gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 150mAh/g.
Embodiment 3. takes by weighing 400g Fe
2O
3, 575.2g NH
4H
2PO
4, 510gCH
3COOLi2H
2O, 7.85g conductive carbon black and 142.6g sucrose, slowly add mass concentration and be in 5% the adipic acid and polyvinyl alcohol mixing aqueous thickener solution, heating and ball-milling mixes solution, form uniform suspension-turbid liquid, resulting suspension-turbid liquid pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1Mpa, and the control temperature of inlet air is 300 ℃, and outlet is 100 ℃, and outlet air separates emptying through the one-level vortex.Spray drying gained powder promptly obtains spherical LiFePO in 900 ℃ of following heat treatments after 8 hours under inert gas shielding
4/ C product.Recording this product tap density is 1.43gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 148mAh/g.
Embodiment 4. and embodiment 1 identical method takes by weighing 400g Fe earlier
2O
3, 660.3g (NH
4)
2HPO
4, 185.93g LiCO
3, 39.25g conductive carbon black and 142.6g sucrose, be the amount weighing magnesium nitrate of Mg/Li=0.5% more in molar ratio, slowly add mass concentration and be in 20% the Polyacrylate thickeners aqueous solution, make the spherical LiFePO that mixes 0.5%Mg by the step identical again with embodiment 1
4/ C product.Recording this product tap density is 1.38gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 152mAh/g.
Embodiment 5. makes the spherical LiFePO that mixes 1%Mn by the method for embodiment 4
4/ C product.Recording this product tap density is 1.39gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 150mAh/g.
Embodiment 6. makes the spherical LiFePO that mixes 2%Zr by the method for embodiment 4
4/ C product.Recording this product tap density is 1.37gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 146mAh/g.
Embodiment 7. makes the spherical LiFePO that mixes 1%Mo by the method for embodiment 4
4/ C product.Recording this product tap density is 1.39gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 149mAh/g.
Embodiment 8. makes the spherical LiFePO that mixes 2%Cr by the method for embodiment 4
4/ C product.Recording this product tap density is 1.38gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 147mAh/g.
Comparing embodiment 1. takes by weighing 16.2g Fe (NO
3)
39H
2O, 1.48g Li
2CO
3, 4.6g NH
4H
2PO
4With 1.36g sucrose ground and mixed evenly after, in nitrogen atmosphere, make LiFePO after 16 hours in 800 ℃ of heat treatments
4/ C product.Recording this product tap density is 1.08gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 132mAh/g.
Do not add carbon black in comparing embodiment 2. raw materials, other is identical with embodiment 1, makes LiFePO
4/ C product.Recording this product tap density is 1.46gcm
-3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density
2Specific discharge capacity when discharging and recharging is 122mAh/g.
Claims (4)
1. anode material for lithium-ion batteries high-density spherical LiFePO
4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion
2O
3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO
4Product quality percentage is 1～5% ultrafine electricity conductive carbon black and mol ratio C: Fe=1: 1 carbon-source cpd;
2) slowly to join mass concentration be in 5%～30% the organic compound aqueous thickener solution, under the heating and ball-milling stirring condition, to make mixed solution form uniform suspension-turbid liquid to the material that step 1) is taken by weighing;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical powder;
4) with the spherical powder of step 3) gained under inert gas shielding in 700 ℃～900 ℃ following heat treatments 8～20 hours, promptly obtain spherical LiFePO
4/ C product.
2. according to the described a kind of anode material for lithium-ion batteries high-density spherical LiFePO of claim 1
4The preparation method of/C is characterized in that: described phosphate compounds is LiH
2PO
4, NH
4H
2PO
4With (NH
4)
2HPO
4In a kind of, Li source compound is CH
3COOLi2H
2O, LiCO
3Or LiOHH
2A kind of among the O, carbon-source cpd is sucrose or glucose; The organic compound thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more.
3. anode material for lithium-ion batteries high-density spherical Li doped FePO
4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion
2O
3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO
4Product quality percentage is 1～5% ultrafine electricity conductive carbon black and mol ratio C: Fe=1: 1 carbon-source cpd is nitrate or the acetate that M/Li=0.5%～2% takes by weighing doped metal ion M more in molar ratio; A kind of among doped metal ion M=Mg, Mn, Zr, Mo or the Cr;
2) slowly to join mass concentration be in 5%～30% the organic compound aqueous thickener solution to the material that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical adulterated powder;
4) with the spherical adulterated powder of step 3) gained under inert gas shielding in 700 ℃～900 ℃ following heat treatments 8～20 hours, promptly obtain spherical Li doped FePO
4/ C product.
4. according to the described a kind of anode material for lithium-ion batteries high-density spherical LiFePO of claim 3
4The preparation method of/C is characterized in that: described phosphate compounds is LiH
2PO
4, NH
4H
2PO
4With (NH
4)
2HPO
4In a kind of, Li source compound is CH
3COOLi2H
2O, LiCO
3Or LiOHH
2A kind of among the O, carbon-source cpd is sucrose or glucose; The organic compound thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more.
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| CN101935072B (en) * | 2010-08-26 | 2014-01-29 | 中国科学院化学研究所 | Ferrous lithium sulphate fluoride as well as preparation method and application thereof |
| CN101948103A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Method for preparing ferrous phosphate radical lithium salt of lithium ion battery |
| CN102139870A (en) * | 2010-12-03 | 2011-08-03 | 清华大学 | Nanocrystal microsphere lithium iron phosphate material with high tap density and preparation method thereof |
| TWI443899B (en) * | 2011-06-22 | 2014-07-01 | Nat Univ Tsing Hua | Lifepo4 powders for li-ion battery and method for manufacturing the same |
| US11476462B2 (en) | 2011-06-22 | 2022-10-18 | National Tsing Hua University | LiFePO4 precursor for manufacturing electrode material of Li-ion battery and method for manufacturing the same |
| CN102244247A (en) * | 2011-06-27 | 2011-11-16 | 上海电力学院 | Preparation method for carbon-encapsulated lithium ion battery cathode material LiFePO4/C |
| CN102263248B (en) * | 2011-06-28 | 2014-01-01 | 清华大学 | Method for preparing carbon coated nanometer LiFePO4 |
| CN102299319A (en) * | 2011-07-20 | 2011-12-28 | 彩虹集团公司 | Preparation method of lithium ion battery anode material LiFePO4 |
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