CN101728526B - Lithium ion battery cathode material and preparation method thereof - Google Patents
Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN101728526B CN101728526B CN2009102414848A CN200910241484A CN101728526B CN 101728526 B CN101728526 B CN 101728526B CN 2009102414848 A CN2009102414848 A CN 2009102414848A CN 200910241484 A CN200910241484 A CN 200910241484A CN 101728526 B CN101728526 B CN 101728526B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims description 26
- 150000004706 metal oxides Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 150000002736 metal compounds Chemical class 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 150000005840 aryl radicals Chemical class 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- -1 transition metal acetate Chemical class 0.000 claims description 5
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 3
- PQTHXJVFTDWEEE-UHFFFAOYSA-N 4-methylpent-3-enal Chemical class CC(C)=CCC=O PQTHXJVFTDWEEE-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 150000001336 alkenes Chemical group 0.000 claims description 3
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
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- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 claims description 2
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- NQLVCAVEDIGMMW-UHFFFAOYSA-N cyclopenta-1,3-diene;cyclopentane;nickel Chemical compound [Ni].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 NQLVCAVEDIGMMW-UHFFFAOYSA-N 0.000 claims description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- FVKGRHSPCZORQC-UHFFFAOYSA-N formaldehyde;toluene Chemical compound O=C.CC1=CC=CC=C1 FVKGRHSPCZORQC-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 2
- 229950009195 phenylpropanol Drugs 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 239000004334 sorbic acid Substances 0.000 claims description 2
- 229940075582 sorbic acid Drugs 0.000 claims description 2
- 235000010199 sorbic acid Nutrition 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims 1
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 6
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 239000007772 electrode material Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
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- 239000011258 core-shell material Substances 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- DBLMXLQJTBGLMP-UHFFFAOYSA-N iron tetracarbonyl hydride Chemical group [Fe].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] DBLMXLQJTBGLMP-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium ion battery cathode material and a preparation method thereof. The cathode material comprises a carbon-coated nano-metal oxide composite material, wherein a carbon-coated nano-metal oxide has a nuclear shell structure, grains are uniformly dispersed, the diameter range of the grains is 10-80nm, and the thickness of a carbon coating is 2.5-10nm. An electrode made of the cathode material has higher reversible capacity and excellent cyclical stability.
Description
Technical field:
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, belong to the electrode material of secondary lithium ion battery field.
Background technology:
Lithium rechargeable battery has high voltage, high specific energy, long-life, advantage such as pollution-free, replaced the main flow that nickel-cadmium cell and Ni-MH battery become commercial secondary cell in the small-sized secondary batteries field, and because the rise at full speed of global oil price, the practicability of electric automobile is subjected to the very big attention of countries in the world, lithium battery will be more and more universal in the application of automobile industry, therefore the chemical power source material had higher requirement.
Compare with the carbon negative pole material (as: native graphite, Delanium) that present industrialization is used, transition metal oxide has very high theoretical specific capacity [Poizot P et al.Nano-sized transition-metal oxides as negative electrode materials for lithium-ionbatteries.Nature 2000 when being used for lithium cell cathode material; 28:407], have low, the environment amenable characteristics of cost simultaneously, cause the extensive concern [Peter GB et al.Nanomaterials for RechargeableLithium Batteries.Lithium Batteries, 2008:47:2-19] of scientific circles and business circles.Yet transition metal oxide change in volume in the charge and discharge cycles process is bigger, has very high irreversible capacity loss, very poor [the YG.Guo et al.Superior electrode performance of nanostructured mesoporousTiO of stable circulation performance
2(Anatase) through efficient hierarchical mixed conducting networks.Adv.Mater.2007,19,2087].Transition metal oxide nanoization can partly be addressed this problem, make that lithium ion is easier to insert and emit between electrode and electrolyte, improve its electrochemistry cycle performance, but along with the increase that discharges and recharges number of times, because the specific area height of nano dot electrode material, be easy between nano particle reunite and cause serious irreversibility, reduction cyclical stability [F.Cheng et al.Template-directed materials for rechargeable Lithium-Ion batteries.Chem.Mater. 2008 then, 20,667].So, increase one deck carbon coating layer on transition metal oxide nano-particles surface and be one of the most effectual way that improves its electrochemistry stable circulation performance [L.J.Fu et al.Surfacemodifications of electrode materials for lithium ion batteries.Electrochem.Commun.2006,8,1].
Carbon coats the transition metal oxide material because oxide particle is subjected to effective protection of coating layer; thereby not only improved the conductivity of oxide material; and, be beneficial to the cyclical stability that improves electrode owing to coat volumetric expansion and mutual reunion that the existence of carbon-coating can suppress the inner casing oxide material well.The preparation method of conventional carbon clad nano metal oxide composite mainly is a hydro thermal method.Hydro thermal method is the method for preparing material by the continuous generation redox reaction in liquid phase of multistep.Generally [LQ.Xu et al.Formation, characterization, and magnetic properties of Fe
3O
4Nanowiresencapsulated in carbon microtubes.J.Phys.Chem.B 2004,108.] all very high (〉=16Mpa of pressure and temperature that adopts of experiment, 〉=600 ℃), product purity is relatively poor (when nano particle forms, also follow the generation of fullerene and carbon nano-tube), complicated process of preparation, output are also very low; With [XM.Sunet al.OxidesC core-shell nanostructures:one-pot synthesis, rational conversion, and Li storage property.Chem.Mater.2006,18.] polysaccharide or glycan be as carbon source, Nano grade metal oxide particle catalyst reaction with high dispersive under high temperature (180～1000 ℃) prepares nano-metal-oxide/material with carbon element, this method often is mixed with gas-phase growth of carbon fibre or carbon nano-tube, the product component complexity, be difficult to separate, productive rate is very little, reaction time is long, and is difficult to realize large-scale production; [Hao Liu et al.Magnetite/carbon core-shell nanorods as anode materials forlithium-ion batteries.Electrochemistry Commun.2008 is 10.] with α-Fe for Liu Hao etc.
2O
3Nanometer rods prepares carbon by hydro thermal method and coats Fe as template
3O
4Obviously this method need prepare nanometer α-Fe in advance
2O
3Template, the step that preparation needs is many, and the preparation process complexity is not suitable for the commercial scale preparation.
Summary of the invention:
One of purpose of the present invention is existing shortcoming during as lithium cell cathode material at transition metal oxide, and a kind of novel cell negative electrode material is provided, and improves its cyclical stability when keeping than height ratio capacity.
A kind of lithium ion battery negative material provided by the invention, for having the carbon-coated nano metal oxide composite of nucleocapsid framework, the particle diameter scope is 10nm～80nm, carbon coating layer thickness is 2.5nm～10nm, Dispersion of Particles is even, and the mass percent of each component is: nano-metal-oxide 20%～60%; Carbon 40～80%.
Another object of the present invention is to provide a kind of method for preparing above-mentioned lithium ion battery negative material.
A kind of method for preparing described lithium ion battery negative material provided by the invention comprises the following steps:
A: be that 1: 0.1～1: 5 oxygen-bearing hydrocarbon mixes with transistion metal compound and organic solvent and is stirred to evenly with mass ratio, dry then.The gained solid is placed autoclave, under inert atmosphere, be warming up to 400～550 ℃, stop immediately heating up, treat that temperature drops to room temperature, obtains thermal decomposition product.
The reaction that is taken place in the A step is the thermal decomposition of oxygen-bearing hydrocarbon, and oxygen-bearing hydrocarbon provides carbon source and oxygen source for final product, and transition metal oxide provides source metal simultaneously as high temperature catalyst; The preferable range of oxygen-bearing hydrocarbon and transistion metal compound mass ratio is 1: 1～1: 4.
Organic solvent is preferably oxolane, acetone, ethanol or benzene, and its consumption fully dissolves in organic solvent with oxygen-bearing hydrocarbon and transistion metal compound and is as the criterion.
B: with pyridine or oxolane be solvent to the thermal decomposition product that the A step obtains clean, filter, drying, obtain target product.
Described oxygen-bearing hydrocarbon is selected from a kind of in alcohol, acid or acid anhydrides, aldehyde, the phenol of a kind of or more than one groups that have aryl radical, alkylene, alkyl, heterocyclic group or the carbohydrate of only being made up of C, H, O.
Alkene or alkane group are meant that carbon number is greater than 4 and less than 30 olefin group or alkane group in the described organic oxygen-containing hydrocarbon.
Wherein have the alcohol of a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group, be preferably: octadecanol, phenylpropanol.
Have the aldehyde of a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group, be preferably: o-methyl-benzene formaldehyde, 4-methyl-3-pentenals, 3-benzenpropanal.
Have the acid or the acid anhydrides of a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group, be preferably: o-toluic acid, crotonic acid, sorbic acid, phthalic anhydride.
Have aryl radical, alkylene, alkyl, heterocyclic group a kind of or more than one groups phenol be preferably: resorcinol, phloroglucin or ortho-methyl phenol.
Only the carbohydrate of being made up of C, H, O is sorbierite, xylitol or glucose.
Described transistion metal compound is selected from a kind of in cyclopentadienyl transition organo-metallic compound, carbonyl transition organo-metallic compound, acetylacetone based transition organo-metallic compound, transition metal acetate or the transition metal nitrate.
Wherein the cyclopentadienyl transistion metal compound is preferably ferrocene, cobaltocene or dicyclopentadienyl nickel.
The carbonyl transistion metal compound is preferably carbonyl iron, carbonyl cobalt or carbonyl nickel.
Acetylacetone based transistion metal compound is preferably ferric acetyl acetonade, nickel acetylacetonate or acetylacetone cobalt.
The transition metal acetate is preferably cobalt acetate, nickel acetate or ferric acetate.
Transition metal nitrate is preferably ferric nitrate, cobalt nitrate or nickel nitrate.
The present invention is owing to adopt the carbon-coated nano metal oxide composite as lithium ion battery negative material, pass through electrochemical property test, reversible capacity is up to 750～1000mAh/g first, after current density is 50mA/g circulation 30 times, capacity can keep 350～500mAh/g, overcome the problem that occurs when transition metal oxide is done negative material effectively, made negative material have higher reversible capacity and good cyclical stability.
Method provided by the invention only need be passed through mixing, carbonization, extraction process just can obtain the carbon-coated nano metal oxide composite, system generally is lower than 10.0Mpa from rising final pressure under mesophilic condition, have characteristics such as technology is simple, the material preparation cost is low, purity is high, the metal types selectable range is wide, easily realize mass preparation.
Description of drawings:
Fig. 1-Fig. 5 is the embodiment of the invention 1 under 450 ℃ of final temperatures, and mass ratio is that 1: 2 the resorcinol and the carbon of ferrocene generation coat Fe
3O
4The resolution chart of nano particle.
Fig. 1 is X-ray diffraction (XRD) figure;
Fig. 2 is thermogravimetric analysis figure;
Fig. 3 is the transmission electron microscope picture;
Fig. 4 is a cycle charge discharge electrograph during as lithium cell cathode material;
Fig. 5 is a first charge-discharge curve during as lithium cell cathode material.
Embodiment:
Below in conjunction with embodiment the present invention is described further, but is not construed as limiting the invention.
Take by weighing at 1: 2 by mass ratio and to analyze pure resorcinol 10g and ferrocene 20g, mixes with the 200ml acetone solvent and be stirred to even, subsequently 40 ℃ carry out water bath with thermostatic control be dried to acetone volatilize fully solid, solid is placed autoclave.Heat under nitrogen protection, heating rate is kept 3 ℃/min, when normal temperature is elevated to 450 ℃, stops to heat up, and treats that temperature drops to normal temperature, obtains thermal decomposition product, and system only reaches 5.0Mpa from the power of boosting.
With the pyridine is solvent, under 120 ℃ of situations of temperature, to thermal decomposition product clean repeatedly, extracting, fade to achromaticity and clarification until filtrate.Filter residue after the oven dry is carbon-coated nano Fe
3O
4Composite material, its yield are 68%.By thermogravimetic analysis (TGA), obtain containing Fe in this material
3O
4Be 39.8%.
The analysis showed that as Fig. 1 X-ray diffraction (XRD) metal oxide particle is Fe
3O
4Show Fe as Fig. 2 thermogravimetric (TG) analysis result
3O
4The quality percentage composition be about 40.0%, the content of carbon is about 60.0%; Carbon-coated nano Fe shown in Fig. 3 transmission electron microscope (TEM)
3O
4The composite material particle diameter has nucleocapsid structure and is dispersed in the carbon base body between 20-60nm.
Electrode adopts coating method to be made.Detailed process is as follows: product, binder PVDF, the acetylene black prepared are mixed by 80: 10: 10 mass ratio, evenly spread upon on the Copper Foil after being modulated into paste with N-2 methyl-pyrrolidones, then in vacuum drying oven 120 ℃ dry 16 hours down, the Copper Foil that will scribble active material at last cuts into disk and makes work electrode.What simulated battery adopted is button CR2032 type system, is metal lithium sheet to electrode wherein.The assembling of simulated battery is finished in the German M. Braun Unilab of company type glove box.The method of testing of battery: for reversible capacity, coulombic efficiency, the cycle performance of investigating material with carbon element and composite material, constant current charge-discharge carries out test analysis in the experiment.The condition of discharging and recharging is: current density is 50mA/g, and voltage range is 0.01-2.5V.Cycle-index is generally 30-50 time.
As shown in Figure 5: as lithium cell cathode material, discharge capacity has reached 960mAh/g first, swathes reversible specific capacity and has reached 449.8mAh/g; As shown in Figure 4 after current density is 50mA/g circulation 30 times, capacity can remain on 375mAh/g, and traditional industrial tri-iron tetroxide is (when particle size range is 100nm～1000nm) as negative material, discharge capacity first can reach 1100mAh/g, after current density was 50mA/g circulation 30 times, capacity only can remain on 145mAh/g.
Embodiment 2
Method of operation is with embodiment 1, take by weighing analysis purified petroleum benzin formaldehyde 10g and acetylacetone based iron 20g at 1: 2 by mass ratio, add and to mix in the 200ml alcohol solvent and be stirred to evenly, subsequently 40 ℃ carry out water bath with thermostatic control be dried to ethanol volatilize fully solid, solid is placed autoclave.Heat under nitrogen protection, heating rate is kept 3 ℃/min, when normal temperature is elevated to 450 ℃, stops immediately heating up, and treats that temperature drops to room temperature, obtains thermal decomposition product, and system finally reaches 6.0Mpa from the power of boosting.
With the pyridine is solvent, under 120 ℃ of situations of temperature, to thermal decomposition product clean repeatedly, extracting, fade to achromaticity and clarification until filtrate.Finally obtain the carbon-coated nano Fe3O4 composite material of particle size distribution between 20-60nm.By thermogravimetic analysis (TGA), obtain in the material, the content of metal oxide is 37.2%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows that this negative material shows good stable circulation performance, and discharge capacity is up to 950mAh/g first, is that 50mA/g circulates after 30 times in current density, and capacity can remain on 368mAh/g.
Embodiment 3
Take by weighing pure M-phthalic acid 10g of analysis and ferrocene 20g at 1: 2 by mass ratio, the method for other step is with embodiment 1.Finally obtain the carbon-coated nano Fe of particle size distribution at 20-80nm
3O
4Composite material by thermogravimetic analysis (TGA), obtains in the material, and the content of metal oxide is 38.3%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows that this negative material shows good stable circulation performance, and discharge capacity is up to 985mAh/g first, is that 50mA/g circulates after 30 times in current density, and capacity can remain on 379mAh/g.
Embodiment 4
Respectively take by weighing 10g at 2: 1 by mass ratio and analyze pure cinnamic acid and ferric nitrate 5g; add and be stirred in the 100ml tetrahydrofuran solvent evenly; under 40 ℃ of waters bath with thermostatic control, carry out subsequently drying until oxolane volatilize fully solid; the gained solid is placed autoclave, heat under nitrogen protection, heating rate is kept 3 ℃/min; when normal temperature is elevated to 550 ℃; stop immediately heating up, treat that temperature drops to room temperature, obtains thermal decomposition product.System's final pressure is 8.0Mpa.
With acetone be solvent at normal temperatures to thermal decomposition product clean repeatedly, extracting, fade to achromaticity and clarification until filtrate.Filter residue after the oven dry is carbon-coated nano Fe
3O
4Composite material, its yield is about 50%.Obtain carbon-coated nano Fe by TEM (transmission electron microscope) analysis
3O
4The composite material particle diameter (between the 30nm～80nm), is having nucleocapsid structure and is being dispersed in the carbon base body; By thermogravimetic analysis (TGA), obtaining metal oxide content is 20.5%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows, is that 50mA/g circulates after 30 times in current density, and capacity can remain on 375mAh/g.
Method of operation is with embodiment 1, and transistion metal compound changes iron tetracarbonyl into, and it is constant to keep other condition, obtains carbon-coated nano Fe
3O
4Composite material.By thermogravimetic analysis (TGA), obtaining metal oxide content is 56%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows, discharge capacity is up to 1340mAh/g first, is that 50mA/g circulates after 30 times in current density, and capacity can remain on 369mAh/g.
Embodiment 6
Take by weighing at 1: 4 by mass ratio and to analyze pure 4-methyl-3-pentenals 10g and ferrocene by 40g, evenly mix, dissolve with the 100ml tetrahydrofuran solvent and to be stirred to evenly, subsequently 40 ℃ carry out water bath with thermostatic control be dried to oxolane volatilize fully solid, solid is placed autoclave.Heat under nitrogen protection, heating rate is kept 3 ℃/min, when normal temperature is elevated to 550 ℃, stops immediately heating up, and treats that temperature drops to room temperature, obtains thermal decomposition product, and system is from boosting power 7.0Mpa.
With the pyridine is solvent, under 120 ℃ of situations of temperature, to thermal decomposition product clean repeatedly, extracting, fade to achromaticity and clarification until filtrate.Filter residue after the oven dry is carbon-coated nano Fe
3O
4Composite material, its yield are 65%.
The analysis showed that through x ray diffraction (XRD) metal oxide particle is Fe
3O
4By carbon-coated nano Fe shown in the transmission electron microscope (TEM)
3O
4The composite material particle diameter has nucleocapsid structure and is dispersed in the carbon base body between 25～70nm.By thermogravimetic analysis (TGA), obtaining metal oxide content is 30.7%.Adopt the method identical to carry out charge-discharge test with embodiment 1, the result shows that its electrochemical property test result shows that as lithium cell cathode material, first discharge specific capacity is up to 785mAh/g, after current density was 50mA/g circulation 50 times, capacity can remain on 305mAh/g.
Embodiment 7
Taking by weighing the pure resorcinol 10g of analysis at 1: 1 by mass ratio evenly mixes with acetylacetone cobalt 10g; evenly mix with 100ml acetone; subsequently 40 ℃ carry out water bath with thermostatic control be dried to acetone volatilize fully solid; solid placed put into autoclave, heat under nitrogen protection, heating rate is kept 3 ℃/min; when normal temperature is elevated to 500 ℃; stop immediately heating up, treat that temperature drops to room temperature, obtains thermal decomposition product.Thermal decomposition product is cleaned repeatedly, filters at 70 ℃ through oxolane again, fade to achromaticity and clarification until filtrate.Filter residue after the oven dry is carbon-coated nano cobalt oxide composite material, and its yield is about 48%.
Metal oxide particle be CoO, average grain diameter about 50nm, be dispersed in the carbon that is undefined structure.By thermogravimetic analysis (TGA), analyzing metal oxide content is 44.2%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows that first discharge specific capacity is 980mAh/g, is to circulate under the 50mA/g after 30 times in current density, and capacity can keep 365mAh/g.And traditional industrial cobalt oxide (when the scope of particle diameter was 100nm～1000nm) as negative material, discharge capacity first reached 1350mAh/g, and after current density was 50mA/g circulation 30 times, capacity can remain on 355mAh/g.
Embodiment 8
Method of operation is with embodiment 7, and it is constant to keep other condition, changes resorcinol into glucose, also obtains carbon-coated nano nanometer cobalt composite material after the reaction, and wherein metal oxide content is 28.5%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows, first discharge specific capacity is up to 855mAh/g, is that 50mA/g circulates after 30 times in current density, and capacity can remain on 326mAh/g.
Embodiment 9
Method of operation is with embodiment 7, and it is constant to keep other condition, and transistion metal compound changes nickel acetylacetonate into, also gets carbon-coated nano nickel oxide composite material by reaction.Wherein metal oxide content is 33.8%.Adopt the method identical with embodiment 1 to carry out charge-discharge test, the result shows that first discharge specific capacity is 784mAh/g, is that 50mA/g circulates after 30 times in current density, and capacity can keep 337mAh/g.And traditional industrial nickel oxide (when the scope of particle diameter was 100nm～1000nm) as negative material, discharge capacity first reached 850mAh/g, and after current density was 50mA/g circulation 30 times, capacity can remain on 145mAh/g.
Claims (6)
1. lithium ion battery negative material, it is characterized in that: described lithium ion battery negative material is the carbon-coated nano metal oxide composite with nucleocapsid framework, the particle diameter scope is 10nm～80nm, carbon coating layer thickness is 2.5nm～10nm, the mass percent of each component is: nano-metal-oxide 20%～60%, carbon 40%～80%;
It is characterized in that: described carbon-coated nano metal oxide composite adopts following method preparation:
A: be that 1: 0.1～1: 5 oxygen-bearing hydrocarbon mixes with transistion metal compound and organic solvent and is stirred to evenly with mass ratio, being dried to organic solvent then volatilizees fully, the gained solid is placed autoclave, in inert atmosphere, be warming up to 400～550 ℃, stop immediately heating up, treat that temperature drops to room temperature, obtains thermal decomposition product;
Described oxygen-bearing hydrocarbon is selected from a kind of in alcohol, acid or acid anhydrides, aldehyde, the phenol of a kind of or more than one groups that have aryl radical, alkylene, alkyl, heterocyclic group; Described transistion metal compound is selected from a kind of in cyclopentadienyl transition organo-metallic compound, carbonyl transition organo-metallic compound, acetylacetone based transition organo-metallic compound, transition metal acetate or the transition metal nitrate;
B: with pyridine or oxolane be solvent to thermal decomposition product clean, filter, drying, obtain target product.
2. the preparation method of a carbon-coated nano metal oxide composite, it is characterized in that: described carbon-coated nano metal oxide composite has the nucleocapsid framework, the particle diameter scope is 10nm～80nm, carbon coating layer thickness is 2.5nm～10nm, the mass percent of each component is: nano-metal-oxide 20%～60%, carbon 40%～80%; Concrete steps and method are:
A: be that 1: 0.1～1: 5 oxygen-bearing hydrocarbon mixes with transistion metal compound and organic solvent and is stirred to evenly with mass ratio, being dried to organic solvent then volatilizees fully, the gained solid is placed autoclave, in inert atmosphere, be warming up to 400～550 ℃, stop immediately heating up, treat that temperature drops to room temperature, obtains thermal decomposition product;
Described oxygen-bearing hydrocarbon is selected from a kind of in alcohol, acid or acid anhydrides, aldehyde, the phenol of a kind of or more than one groups that have aryl radical, alkylene, alkyl, heterocyclic group; Described transistion metal compound is selected from a kind of in cyclopentadienyl transition organo-metallic compound, carbonyl transition organo-metallic compound, acetylacetone based transition organo-metallic compound, transition metal acetate or the transition metal nitrate;
B: with pyridine or oxolane be solvent to thermal decomposition product clean, filter, drying, obtain target product.
3. according to the preparation method of the described carbon-coated nano metal oxide composite of claim 2, it is characterized in that: described oxygen-bearing hydrocarbon and transistion metal compound mass ratio are 1: 1～1: 4.
4. according to the preparation method of the described carbon-coated nano metal oxide composite of claim 2, it is characterized in that: the carbon number of olefin group or alkane group is greater than 4 and less than 30 in the described oxygen-bearing hydrocarbon.
5. according to the preparation method of the described carbon-coated nano metal oxide composite of claim 2, it is characterized in that: described cyclopentadienyl transistion metal compound is ferrocene, cobaltocene or dicyclopentadienyl nickel, the carbonyl transistion metal compound is carbonyl iron, carbonyl cobalt or carbonyl nickel, acetylacetone based transistion metal compound is nickel acetylacetonate or acetylacetone cobalt, the transition metal acetate is cobalt acetate, nickel acetate or ferric acetate, and transition metal nitrate is ferric nitrate, cobalt nitrate or nickel nitrate.
6. according to the preparation method of claim 2 or 4 described carbon-coated nano metal oxide composites, it is characterized in that: the alcohol that has a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group is octadecanol, phenylpropanol; The aldehyde that has a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group is o-methyl-benzene formaldehyde, 4-methyl-3-pentenals or 3-benzenpropanal; The acid or the acid anhydrides that have a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group are o-toluic acid, laurate, cinnamic acid, sorbic acid, crotonic acid or phthalic anhydride; The phenol that has a kind of or more than one groups of aryl radical, alkylene, alkyl, heterocyclic group is resorcinol, phloroglucin or ortho-methyl phenol.
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| CN102024938B (en) * | 2010-10-29 | 2013-04-24 | 北京工业大学 | C/Fe3C lithium ion battery negative material and preparation method thereof |
| CN102185142A (en) * | 2011-04-08 | 2011-09-14 | 厦门大学 | Composite carbon cathode material for lithium ion battery and preparation method thereof |
| CN102509786B (en) * | 2011-10-11 | 2013-11-20 | 北京化工大学 | Porous metal oxide-carbon composite thin film electrode and preparation method thereof |
| CN102610809B (en) * | 2012-03-14 | 2014-11-26 | 北大先行科技产业有限公司 | Ferroferric oxide/graphite lithium ion battery anode material and preparation method for ferroferric oxide/graphite lithium ion battery anode material |
| CN102820465B (en) * | 2012-06-20 | 2015-04-01 | 中南大学 | Application of polyacrylic acid in preparation of lithium ion battery anode material nano-sized iron oxide/carbon composite material |
| CN102790217B (en) * | 2012-07-26 | 2014-07-09 | 天津大学 | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof |
| CN103094551B (en) * | 2012-08-24 | 2016-03-23 | 中国科学院上海硅酸盐研究所 | A kind of graphite/manganous oxide combination electrode material and preparation method thereof |
| CN103647041A (en) * | 2013-12-10 | 2014-03-19 | 浙江大学 | Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery |
| CN103794762B (en) * | 2014-01-23 | 2016-03-23 | 上海海事大学 | The low-temperature oxidation preparation method that the coated variety classes of a kind of carbon is nanocrystalline |
| JP6428244B2 (en) * | 2014-12-19 | 2018-11-28 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery manufacturing method and non-aqueous electrolyte secondary battery |
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| CN108788181B (en) * | 2018-07-10 | 2021-07-06 | 哈尔滨理工大学 | Method for synthesizing core-shell structure carbon-coated gold nanoparticles with regular spherical morphology |
| CN109616626B (en) * | 2018-11-15 | 2022-02-15 | 上海海事大学 | Low-temperature macro preparation method of carbon-coated ferroferric oxide nanocrystal |
| CN111468126A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite containing alkali metal, and preparation method and application thereof |
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Effective date of registration: 20210105 Address after: 100020 d-2-8 (1-3 floors), Beijing Hongzhuang international cultural bonded Innovation Park, No.1, baijialou, Chaoyang North Road, Chaoyang District, Beijing Patentee after: BEIJING HUAKE XUNNENG GRAPHENE NEW TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 100000 Hongzhuang International Cultural Bonded Innovation Park D-2-6, No. 1 Baijialou Jia, Chaoyang North Road, Chaoyang District, Beijing Patentee before: Xiao Yanshe |