CN101604743A - Composite cathode material for lithium ion cell and preparation method - Google Patents
Composite cathode material for lithium ion cell and preparation method Download PDFInfo
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- CN101604743A CN101604743A CNA2009100673373A CN200910067337A CN101604743A CN 101604743 A CN101604743 A CN 101604743A CN A2009100673373 A CNA2009100673373 A CN A2009100673373A CN 200910067337 A CN200910067337 A CN 200910067337A CN 101604743 A CN101604743 A CN 101604743A
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- natural graphite
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- hard carbon
- lithium ion
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 230000003068 static effect Effects 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 235000021463 dry cake Nutrition 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007614 solvation Methods 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
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- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of composite cathode material for lithium ion cell and preparation method, wherein contain heteroatomic hard carbon persursor material, selecting raw material for use is wherein one or more of phenolic resins, poly-furfural, furane resins, polyvinyl alcohol, epoxy resin or polyacrylonitrile, account for spherical natural graphite mass percent 5%-45%, heteroatomic modifier is boracic modified dose and comprises boric acid, diboron trioxide; Phosphorous modifier comprises phosphoric acid, phosphorus pentoxide; Nitrogenous modifier HNO
3Wherein a kind of accounts for hard carbon presoma mass percent 5%-35%; Spherical natural graphite; The negative material of the present invention's preparation is formed simulated battery, and the capacity of gained battery surpasses 350mAH/g, and enclosed pasture efficient reaches 95.8% first, and excellent cycle performance is arranged.Be that a kind of cost is low, the simple method of technology.
Description
Technical field
The present invention relates to a kind of composite cathode material for lithium ion cell and preparation method.
Background technology
Lithium ion battery has high energy density, high open circuit voltage, good security performance.Because lithium ion battery has these advantages, lithium ion battery has been subjected to people's extensive concern always since coming out.The electrode material of the lithium ion battery of people's research now has metal oxide and material with carbon element.Wherein material with carbon element has low voltage platform, and higher specific capacity, these advantages of particularly low cost are expanded the application of material with carbon element in lithium ion cell electrode.But it and electrolyte compatibility are poor, the solvation molecule takes place during charging easily enter graphite linings, and graphite linings is peeled off, and electrolyte and graphite linings continue to react, and cause the cycle performance variation of graphite material.Therefore graphite material is used and is restricted, so need carry out modification to graphite material.
The method of at present common employing is that carbon coats method, people such as Yu Shiang Wu have reported on the Journal of Alloys and Compounds 426:218-222 in 2006 with this hard carbon coated natural graphite of phenolic resins, they have well solved the cycle performance of graphite cathode composite material, but, in their preparation technology, in hard carbon, do not add and contain heteroatomic additive, this has caused prepared composite material enclosed pasture is most effective first also being lower than 90%, can't reach commercial use, these have limited hard carbon and have coated the application of spherical natural graphite as lithium ion battery.
Summary of the invention
Goal of the invention provides a kind of composite cathode material for lithium ion cell;
Another purpose of invention provides a kind of preparation method of composite cathode material for lithium ion cell.
Coat based on hard carbon on the basis of spherical natural graphite, in hard carbon, introduce hetero-atom, coat spherical graphite and improve on the basis of good cycle performance having kept phenolic resins cracking carbon, improve the efficient of enclosed pasture first of spherical natural graphite.
Composite cathode material for lithium ion cell of the present invention, wherein contain heteroatomic hard carbon persursor material, selecting raw material for use is wherein one or more of phenolic resins, poly-furfural, furane resins, polyvinyl alcohol, epoxy resin or polyacrylonitrile, account for spherical natural graphite mass percent 5%-45%, heteroatomic modifier is boracic modified dose and comprises boric acid, diboron trioxide; Phosphorous modifier comprises phosphoric acid, phosphorus pentoxide; Nitrogenous modifier HNO
3Wherein a kind of accounts for hard carbon presoma mass percent 5%-35%; Spherical natural graphite;
Preparation process is as follows:
1), with wherein one or more of phenolic resins, poly-furfural, furane resins, polyvinyl alcohol, epoxy resin or polyacrylonitrile; Heteroatomic modifier, boracic modified dose comprises boric acid, diboron trioxide, phosphorous modifier comprises phosphoric acid, phosphorus pentoxide, nitrogenous modifier HNO
3, wherein a kind of; Take by weighing by mass percentage, be dissolved in ethanol and stir;
2), add native graphite, constant temperature 50-90 ℃ of continuation stirring 1-5h;
3), with the static 1-4h of reactant, filter filter cake;
4), with filter cake 80-120 ℃ of following vacuumize;
5), filter cake is put into heating furnace, at inert gas N
2Or the Ar protection down, rises to 600-1300 ℃ with 1-10 ℃/min speed, and insulation 0.5-5h naturally cools to room temperature, and the product of gained is pulverized, and promptly gets the spherical natural graphite composite material that contains the coating of hetero-atom hard carbon.
With the negative material of the present invention's preparation, form simulated battery, the capacity of gained battery surpasses 360mAH/g, and enclosed pasture efficient reaches 95.8% first, and excellent cycle performance is arranged.
The present invention is by having added hetero-atom in graphite surface hard carbon coating layer, heteroatomic introducing has changed the structure of surperficial hard carbon, and the change of this structure has reduced composite material because the reduction of the coulombic efficiency first that the introducing of hard carbon causes.Therefore, preparation technology of the present invention has further improved the efficient of enclosed pasture first of material in the cycle performance that has improved graphite.Be that a kind of cost is low, the simple method of technology.
Embodiment
For clearer explanation the present invention, enumerate following example, but its to the present invention without any restriction.
Embodiment 1
Take by weighing the 10g spherical natural graphite, the phenolic resins quality is a spherical natural graphite 15%, phosphoric acid quality is 35% of a phenolic resins quality, and phenolic resins is dissolved in ethanol, adds phosphoric acid and stirs, add spherical natural graphite, constant temperature continues to stir 1h for 50 ℃, and static 1h filters filter cake, under 80 ℃ in vacuum, dry cake is standby.Put into heating furnace, at N
2Following protection rises to 600 ℃ with 1 ℃/min, and insulation 0.5h naturally cools to room temperature, obtains composite cathode material for lithium ion cell.
Embodiment 2
Take by weighing the 40g spherical natural graphite, the furane resins quality is 12.5% of a spherical natural graphite, furane resins are dissolved in ethanol, adding the boric acid quality is 20% of furane resins, and the back that stirs adds spherical natural graphite, and constant temperature continues to stir 4h for 90 ℃, static 4h, filter filter cake, under 120 ℃ in vacuum, dry cake is standby.Put into heating furnace, under Ar protection, be warmed up to 1300 ℃ of insulation 3h, naturally cool to room temperature, obtain composite cathode material for lithium ion cell with the speed of 10 ℃/min.
Embodiment 3
Take by weighing the 30g spherical natural graphite, the epoxy resin quality is 10% of a spherical natural graphite, and epoxy resin is dissolved in ethanol; adding the diboron trioxide quality is 25% of epoxy resin, and the back that stirs adds spherical natural graphite, and constant temperature continues to stir 2h for 85 ℃; static 3h filters filter cake, under 90 ℃ in vacuum; dry cake is standby; put into heating furnace, under Ar protection, be warmed up to 750 ℃ of insulation 3h with the speed of 5 ℃/min; naturally cool to room temperature, obtain composite cathode material for lithium ion cell.
Embodiment 4
Take by weighing the 25g spherical natural graphite, poly-furfural quality is 5% of a spherical natural graphite, will gather furfural and be dissolved in ethanol, adds the nitric acid quality and is 32% of poly-furfural, back adding spherical natural graphite stirs, constant temperature continues to stir 2.5h for 80 ℃, and static 3.5h filters filter cake, under 100 ℃ in vacuum, dry cake is standby, puts into heating furnace, at N
2Following protection is warmed up to 800 ℃ of insulation 3.5h with the speed of 6 ℃/min, naturally cools to room temperature, obtains composite cathode material for lithium ion cell.
Embodiment 5
Take by weighing the 15g spherical natural graphite, the polyvinyl alcohol quality is 45% of a spherical natural graphite, and polyvinyl alcohol is dissolved in ethanol, and adding the phosphorus pentoxide quality is 14.8% of polyvinyl alcohol quality, back adding spherical natural graphite stirs, constant temperature stirs 3.5h for 75 ℃, and static 3.5h filters filter cake, under 110 ℃ in vacuum, dry cake is standby, puts into heating furnace, at N
2Following protection is warmed up to 900 ℃ of insulation 2.5h with the speed of 3 ℃/min, naturally cools to room temperature, obtains composite cathode material for lithium ion cell.
Embodiment 6
Take by weighing the 25g spherical natural graphite, the polyacrylonitrile quality is 6% of a spherical natural graphite quality, and polyacrylonitrile is dissolved in ethanol, and adding the nitric acid quality is 5% of polyacrylonitrile, back adding spherical natural graphite stirs, constant temperature stirs 2h for 70 ℃, and static 3h filters filter cake, under 105 ℃ in vacuum, dry cake is standby, puts into heating furnace, at N
2Following protection is warmed up to 1200 ℃ of insulation 1.5h with the speed of 5 ℃/min, naturally cools to room temperature, obtains composite cathode material for lithium ion cell.
Embodiment 7
Take by weighing the 20g spherical natural graphite, phenolic resins, the furane resins quality is respectively 10% of spherical natural graphite quality, and phosphoric acid quality is 17.5% of phenolic resins and a furane resins gross mass, phenolic resins and furane resins are dissolved in ethanol, add phosphoric acid and stir, add spherical natural graphite, constant temperature continues to stir 4h for 50 ℃, static 3.5h, filter filter cake, under 80 ℃ in vacuum, dry cake is standby.Put into heating furnace, at N
2Following protection rises to 650 ℃ with 1 ℃/min, and insulation 1.5h naturally cools to room temperature, obtains composite cathode material for lithium ion cell.
Embodiment 8
Take by weighing the 35g spherical natural graphite, phenolic resins, epoxy resin, poly-furfural quality is respectively 5%, 6%, 7% of spherical natural graphite quality, phosphoric acid quality is 23% of three kinds of hard carbon presoma gross masses, and phenolic resins is dissolved in ethanol, adds phosphoric acid and stirs, add spherical natural graphite, constant temperature continues to stir 1h for 50 ℃, and static 1h filters filter cake, under 80 ℃ in vacuum, dry cake is standby.Put into heating furnace, at N
2Following protection rises to 1150 ℃ with 7 ℃/min, and insulation 2.5h naturally cools to room temperature, obtains composite cathode material for lithium ion cell.
Comparing embodiment 1
Original spherical natural graphite does not carry out any modification.
Comparing embodiment 2
Take by weighing the 10g spherical natural graphite, 1.5g phenolic resins is dissolved in ethanol with phenolic resins, adds spherical natural graphite, and constant temperature continues to stir 1h for 50 ℃, and static 1h filters filter cake, and under 80 ℃ in vacuum, dry cake is standby.Put into heating furnace, at N
2Following protection rises to 600 ℃ with 1 ℃/min, and insulation 0.5h naturally cools to room temperature, obtains composite cathode material for lithium ion cell.Electrochemical property test
As negative pole, cobalt acid lithium is formed simulated battery as positive electrode, carries out charge-discharge test under the 0.2C condition with above-mentioned prepared composite material.
The electrochemical property test result
| Sequence number | Initial charge specific capacity (mAH/g) | First discharge specific capacity (mAH/g) | First charge-discharge efficiency (%) | 50 circulation back capacity confining forces (%) |
| Embodiment 1 | 378 | 362 | 95.8 | 97.2 |
| Embodiment 2 | 387 | 358 | 92.4 | 95.8 |
| Embodiment 3 | 377 | 353 | 93.6 | 94.3 |
| Embodiment 4 | 381 | 351 | 92.1 | 96.1 |
| Embodiment 5 | 392 | 368 | 93.9 | 93.9 |
| Embodiment 6 | 371 | 352 | 94.9 | 92.3 |
| Embodiment 7 | 368 | 357 | 97.1 | 90.9 |
| Embodiment 8 | 375 | 360 | 96.0 | 93.7 |
| Comparative example 1 | 412 | 278 | 67.5 | 57.3 |
| Comparative example 2 | 382 | 340 | 88.9 | 89.3 |
When having kept after test result is mixed as can be seen hard carbon to coat the advantage of spherical natural graphite, improved enclosed pasture efficient first simultaneously.
Claims (2)
1, a kind of composite cathode material for lithium ion cell, wherein contain heteroatomic hard carbon persursor material, selecting raw material for use is wherein one or more of phenolic resins, poly-furfural, furane resins, polyvinyl alcohol, epoxy resin or polyacrylonitrile, account for spherical natural graphite mass percent 5%-45%, heteroatomic modifier is boracic modified dose and comprises boric acid, diboron trioxide; Phosphorous modifier comprises phosphoric acid, phosphorus pentoxide; Nitrogenous modifier HNO
3Wherein a kind of accounts for hard carbon presoma mass percent 5%-35%; Spherical natural graphite.
2, a kind of preparation method of composite cathode material for lithium ion cell, wherein contain heteroatomic hard carbon persursor material, selecting raw material for use is wherein one or more of phenolic resins, poly-furfural, furane resins, polyvinyl alcohol, epoxy resin or polyacrylonitrile, account for spherical natural graphite mass percent 5%-45%, heteroatomic modifier is boracic modified dose and comprises boric acid, diboron trioxide; Phosphorous modifier comprises phosphoric acid, phosphorus pentoxide; Nitrogenous modifier HNO
3Wherein a kind of accounts for hard carbon presoma mass percent 5%-35%; Spherical natural graphite; Preparation process is as follows:
1), with wherein one or more of phenolic resins, poly-furfural, furane resins, polyvinyl alcohol, epoxy resin or polyacrylonitrile; Heteroatomic modifier, boracic modified dose comprises boric acid, diboron trioxide, phosphorous modifier comprises phosphoric acid, phosphorus pentoxide, nitrogenous modifier HNO
3, wherein a kind of; Take by weighing by mass percentage, be dissolved in ethanol and stir;
2), add native graphite, constant temperature 50-90 ℃ of continuation stirring 1-5h;
3), with the static 1-4h of reactant, filter filter cake;
4), with filter cake 80-120 ℃ of following vacuumize;
5), filter cake is put into heating furnace, at inert gas N
2Or the Ar protection down, rises to 600-1300 ℃ with 1-10 ℃/min speed, and insulation 0.5-5h naturally cools to room temperature, and the product of gained is pulverized, and promptly gets the spherical natural graphite composite material that contains the coating of hetero-atom hard carbon.
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| CN102231434A (en) * | 2011-05-20 | 2011-11-02 | 河南思维能源材料有限公司 | Modified natural graphite material used in lithium ion battery negative electrodes, and preparation method thereof |
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| CN105070916A (en) * | 2015-09-08 | 2015-11-18 | 湖南星城石墨科技股份有限公司 | Preparation method of highly compacted carbon-coated natural graphite material |
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