CN103022463A - Manganese-based compound cathode material of lithium battery and preparation method of material - Google Patents
Manganese-based compound cathode material of lithium battery and preparation method of material Download PDFInfo
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- CN103022463A CN103022463A CN2012105579346A CN201210557934A CN103022463A CN 103022463 A CN103022463 A CN 103022463A CN 2012105579346 A CN2012105579346 A CN 2012105579346A CN 201210557934 A CN201210557934 A CN 201210557934A CN 103022463 A CN103022463 A CN 103022463A
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- Prior art keywords
- graphene
- negative pole
- lithium
- composite negative
- pole material
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- 239000011572 manganese Substances 0.000 title claims abstract description 132
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 128
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000463 material Substances 0.000 title claims abstract description 105
- 150000001875 compounds Chemical class 0.000 title claims abstract description 80
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 126
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 119
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000007787 solid Substances 0.000 claims abstract description 46
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims description 92
- 239000010936 titanium Substances 0.000 claims description 59
- 229910052719 titanium Inorganic materials 0.000 claims description 59
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 13
- 239000002114 nanocomposite Substances 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 239000008247 solid mixture Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 238000000713 high-energy ball milling Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract 3
- -1 graphene compound Chemical class 0.000 abstract 1
- 150000002642 lithium compounds Chemical class 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 150000003609 titanium compounds Chemical class 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- USEGOPGXFRQEMV-UHFFFAOYSA-N fluoro hypofluorite titanium Chemical compound [Ti].FOF USEGOPGXFRQEMV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229960001841 potassium permanganate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer 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
Abstract
The invention relates to a manganese-based compound cathode material of a lithium battery and a preparation method of the material, and belongs to the technical field of cathode materials of lithium ion batteries. The manganese-based compound cathode material comprises micro-particles of 20-200 nm and adopts a solid Mn3O4/graphene compound cathode material prepared by adopting a manganese compound and grapheme, and an Mn3O4/graphene/lithium titanate nanometer compound cathode material prepared by a lithium compound and a titanium compound. According to the invention, the Mn3O4/graphene is covered with lithium titanate, so that residual oxygen-containing functional groups in the graphene are isolated from an electrolyzing solution, the initial efficiency of the material is improved, the cycle life of the material is prolonged, and the safety of the battery is enhanced; and the cathode material disclosed by the invention has the advantages of high specific capacity, high initial efficiency, excellent rate performance, low irreversible capacity, good safety and long cycle life, and meets the demands of novel lithium ion battery sets.
Description
Technical field
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, more particularly, the present invention relates to a kind of lithium battery manganese base composite negative pole material and preparation method thereof, belong to the lithium ion battery negative material technical field.
Background technology
At present, in the Portable digital product field, lithium rechargeable battery has occupied the leading position in market.And along with electric motor car, the on a large scale rise of energy-storage system, lithium rechargeable battery is large with its energy density, operating voltage is high, have extended cycle life, pollution-free, the advantage such as security performance is good, represent widely application prospect, more and more be subject to the attention of researcher and enterprise.New demand and new challenge have also been brought in new market, and except fail safe, economy, cycle life, the further raising of the energy density of lithium ion battery also seems extremely urgent.
The raising of lithium cell cathode material capacity is one of key of lithium ion battery energy density raising.In general, lithium cell cathode material is divided into charcoal negative pole and non-charcoal negative pole two large classes.Wherein, carbon cathode material especially graphite carbon negative material causes worldwide broad research and exploitation with its structural stability and good cycle performance highly, becomes the lithium ion battery negative material that occupies at present mainstream market.But its theoretical capacity only has 372mAh/g, and ripe graphite cathode capacity can reach more than the 360mAh/g in the market, has substantially reached the limit of development, requirement that more and more can not the satisfying the market development.Therefore, researcher's attentiveness begins to transfer on other material, such as hard charcoal, charcoal/silicon composite, metal oxide etc.
In the middle of numerous research objects, Mn
3O
4More promising a kind of.Mn
3O
4Having theoretical capacity up to 936mAh/g as lithium ion battery negative material, is three times of conventional graphite negative pole.And the reserves of manganese element are abundanter, and bio-toxicity is also very low, so Mn
3O
4It is a kind of up-and-coming lithium cell negative pole material.But, since Mn
3O
4Conductivity is very low, only is 10
-7-10
-8S/cm, the therefore embedding of lithium ion and take off all difficulties relatively of embedding in charge and discharge process has limited the performance of this material capacity.In order to improve Mn
3O
4Charge-discharge performance, the researcher has carried out a large amount of research, such as nanometer and element doping, with Mn
3O
4Charge/discharge capacity be promoted to about 400mAh/g but this and Mn
3O
4Theoretical capacity certain gap is still arranged.
Graphene (Graphene) is a kind of new material of the individual layer laminated structure that is made of carbon atom.Its electron mobility surpasses 15000 cm under the normal temperature
2/ Vs, again ratio nano carbon pipe or silicon wafer height, and resistivity about 10-6 Ω cm only is lower than copper or silver are the present material of resistivity minimum in the world.Therefore, if can be with Mn
3O
4Compound with Graphene, can utilize the good electric conductivity of Graphene to form the space conductive network, greatly improve Mn
3O
4The bottleneck problem of low conductivity promotes the diffusion of lithium ion in the charge and discharge process, improves capacity and the high rate performance of electrode material.
It is 201010237027.4 that State Intellectual Property Office discloses an application number in 2012.2.1, name is called the patent of invention of " transition metal oxide/graphene nanometer composite electrode material used for lithium battery and preparation method thereof ", this patent relates to a kind of transition metal oxide/graphene nanometer composite electrode material used for lithium battery and preparation method thereof, it is the transition metal oxide of Graphene or graphene oxide modification, mode with physically encapsulation or chemical bonding between transition metal oxide and Graphene or the graphene oxide is connected, adopt a kind of in the following method: 1. will prepare the required precursor of transition metal oxide and Graphene (or graphene oxide) and be by weight and to 50: 100 in solvent evenly mix at 0.01: 100, in uniform temperature, reaction obtains nanometer combined electrode material under the pressure; 2. be to 50: 100 in solvent fully to mix at 0.01: 100 by weight with Graphene (or graphene oxide) and transition metal oxide, drying obtains nanometer combined electrode material.The preparation method is easy, easy to operate, is applicable to large-scale production, and the electrode material that makes has the conductivity of higher lithium ion and electronics, and the lithium battery specific capacity of assembling is high, good cycle, is suitable for electrode material of lithium battery.
In the above-mentioned patent, because Graphene is all obtained by the graphene oxide reduction, can introduce inevitably some oxygen-containing functional groups, such as carbonyl, carboxyl, nitro etc., this patent synthesis temperature is not higher than 200 ℃ in addition, and decomposition reaction can not occur these oxygen-containing functional groups in the low-temp reaction, residual oxygen-containing functional group understands in the circulating battery process and electrolyte reacts, the first efficient that this not only can reduce battery affects the cycle life of battery, more can bring potential safety hazard to battery.
Summary of the invention
The present invention is intended to solve the battery that transition metal oxide/graphene nanometer composite electrode material used for lithium battery of the prior art makes, and efficient is low first, battery cycle life is low, and the problem that potential safety hazard is arranged, a kind of lithium battery manganese base composite negative pole material is provided, its specific capacity is large, and efficient is high first, and high rate performance is good, irreversible capacity is low, and fail safe and cycle life are good.
Another object of the present invention provides a kind of optimization preparation method of above-mentioned negative material.
In order to realize the foregoing invention purpose, its concrete technical scheme is as follows:
A kind of lithium battery manganese base composite negative pole material is characterized in that: described lithium battery manganese base composite negative pole material is the particulate of 20-200nm, and described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 20:1-2:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 3:5-5:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 10:1-100:1.
Described Graphene is the commercially available prod, also can use natural flake graphite to be raw material, adopts the standby graphene oxide of general known Hummers legal system.
Describedly contain the manganese compound that contains that manganese compound is this area routine, as: any one in manganese acetate, manganese nitrate, potassium permanganate, manganese sulfate, manganese chloride, potassium manganate, manganous hydroxide or the manganese oxalate.
Described lithium-containing compound is the lithium-containing compound of this area routine, such as in lithium hydroxide, lithium oxalate, lithium acetate, lithium carbonate, lithia, lithium sulfate, lithium nitrate or the lithium chloride any one.
Preferably, described lithium-containing compound is lithium carbonate.
Described titanium-containing compound is titanyl compound, titanium salt or the titanium simple substance of this area routine, as: any one in titanium tetrachloride, butyl titanate, isopropyl titanate, titanium sulfate, titanyl sulfate, difluoro oxygen titanium or the metal titanium sheet; The particle diameter of described titanium-containing compound is 10～1000nm of this area routine.
Preferably, the particle diameter of described titanium-containing compound is 50nm.
A kind of preparation method of lithium battery manganese base composite negative pole material is characterized in that: comprise following processing step:
A, will contain manganese compound and be dissolved in the solvent, what be mixed with mass concentration and be 1-10% contains manganese compound solution;
B, by containing manganese compound and Graphene mass ratio 20:1-2:1 takes by weighing Graphene, join containing in the manganese compound solution that steps A obtains, fully stir, obtain mixed solution;
C, in step B, obtain mixed solution and dripping ammoniacal liquor, regulate pH to 8-10, and stirring reaction 1-5h, Mn obtained
3O
4/ Graphene mixed liquor;
D, the Mn that step C is obtained
3O
4/ Graphene mixed liquor reacts complete rear cooling at 150-200 ℃ of lower reaction 1-5h, obtains reactant liquor;
E, the reactant liquor that uses the method treatment step D of centrifugal, filtration or suction filtration to obtain, with solvent wash 3-5 time, drying obtains solid Mn with the precipitation that obtains
3O
4/ Graphene composite negative pole material;
F, take by weighing lithium-containing compound and titanium-containing compound by elemental lithium and titanium elements atomic ratio 3:5-5:5, then according to solid Mn
3O
4/ Graphene composite negative pole material and titanium-containing compound mass ratio 10:1-100:1 take by weighing solid Mn
3O
4/ Graphene composite negative pole material evenly mixes three kinds of solids, and adopts conventional high-energy ball milling to disperse, and obtains lithium-containing compound, titanium-containing compound and solid Mn
3O
4The solid mixture of/Graphene composite negative pole material;
G, get the solid mixture that obtains in the step F and put into heating furnace, the heating rate with 0.1-1 ℃/min under inert atmosphere rises to 600-1000 ℃, and then heat treated 0.2-5h is cooled to room temperature under inert atmosphere, obtain Mn of the present invention
3O
4/ Graphene/lithium titanate nano composite anode material is lithium battery manganese base composite negative pole material.
Preferably, the solvent of the present invention in steps A and step e is any one in water, ethanol, acetone, formic acid, n-hexane or the toluene.
Preferably, the present invention refers at 0-80 ℃ that in the stirring described in step B and the step C rotating speed is to stir under the 100-1500r/min.
Preferably, the present invention is in step D, and the described 1-5h that reacts under 150-200 ℃ refers to react in water heating kettle.
In step G, described heating furnace is conventional tube furnace, box type furnace or rotary furnace.
Preferably, the present invention is in step G, and described heating furnace is rotary furnace.
In step G, described inert atmosphere is conventional nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
Preferably, the present invention is in step G, and described inert atmosphere is nitrogen atmosphere.
A kind of lithium battery that adopts above-mentioned lithium battery manganese base composite negative pole material to make.
The above-mentioned method for preparing lithium battery is this area common process.
The useful technique effect that the present invention brings:
1, lithium titanate (chemical formula Li4Ti5O12) is a kind of lithium cell cathode material newly developed in recent years.Lithium titanate is 1.55V with respect to the current potential of lithium electrode, far above graphite and hard carbon material, so the first efficient of lithium titanate anode is higher than 95%, and lithium metal can not occur in charge and discharge process yet separates out, can improve the security performance of battery, the present invention uses the lithium titanate shell with Mn
3O
4Wrap up with Graphene, can greatly improve first efficient, cycle life and the security performance of material, material of the present invention has overcome Mn
3O
4The shortcoming of low conductivity makes Mn
3O
4Capacity has obtained fully playing, and has good cyclical stability, good high rate performance and fail safe.
2, the cost of material used of the present invention is cheap, and the source is abundant, is easy to realize large-scale industrial production; The composite material of the present invention's preparation is with Mn
3O
4Be main body, therefore possess Mn
3O
4Height ratio capacity; The composite material of the present invention's preparation has the three-dimensional conductive network that Graphene forms, and utilizes the conduction of building as electronics of solid spacial framework that good passage is provided, thereby has overcome Mn
3O
4Low conductivity, be conducive to Mn
3O
4The performance of capacity also has good high rate performance simultaneously;
3, preparation technology of the present invention makes the most of pyrolysis of oxygen-containing functional group residual in the Graphene by the above sintering step of 600 degree, greatly reduces the oxygen-containing functional group in the Graphene;
4, technique prepares Mn routinely
3O
4, obtain pure Mn
3O
4, this material 1C discharge capacity only has 330mAh/g, and efficient only is 30% first, and namely decays to after 50 times below the 130mAh/g, obtains Mn by technique of the present invention
3O
4/ graphene composite material, this material 1C discharge capacity reaches 930mAh/g, but efficient only has 70% first, and namely decay to after 100 times below the 530mAh/g, as a comparison, after tested, the Mn of the present invention's preparation
3O
4/ Graphene/lithium titanate composite negative pole material is the particulate of 20-200nm, this composite material first capacity can reach 890mAh/g, efficient 90% first, 100 circulations are without obviously decay, through 1000 circulation volume conservation rates more than 90%, and capacity still is not less than 500mAh/g in the large multiplying power discharging situation of 5C, has shown good high rate performance;
5, the present invention uses lithium titanate to Mn
3O
4/ Graphene coats, thereby remaining oxygen-containing functional group and electrolyte in the Graphene are kept apart, and has improved the first fail safe of efficient, cycle life and battery of material; It is large that negative material disclosed by the invention has specific capacity, and efficient is high first, and high rate performance is good, and irreversible capacity is low, and the advantage that fail safe and cycle life are good has been agreed with the right demand of new type lithium ion battery.
Embodiment
Embodiment 1
A kind of lithium battery manganese base composite negative pole material, described lithium battery manganese base composite negative pole material is the particulate of 20nm, described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 2:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 3:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 10:1.
Embodiment 2
A kind of lithium battery manganese base composite negative pole material, described lithium battery manganese base composite negative pole material is the particulate of 200nm, described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 20:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 5:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 100:1.
Embodiment 3
A kind of lithium battery manganese base composite negative pole material, described lithium battery manganese base composite negative pole material is the particulate of 110nm, described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 11:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 4:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 55:1.
Embodiment 4
A kind of lithium battery manganese base composite negative pole material, described lithium battery manganese base composite negative pole material is the particulate of 90nm, described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 3:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 4.5:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 85:1.
Embodiment 5
A kind of lithium battery manganese base composite negative pole material, described lithium battery manganese base composite negative pole material is the particulate of 20-200nm, described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 20:1-2:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 3:5-5:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 10:1-100:1.
Preferably:
Described lithium-containing compound is lithium carbonate.
The particle diameter of described titanium-containing compound is 50nm.
Embodiment 6
A kind of preparation method of lithium battery manganese base composite negative pole material comprises following processing step:
A, will contain manganese compound and be dissolved in the solvent, be mixed with mass concentration and be 1% contain manganese compound solution;
B, by containing manganese compound and Graphene mass ratio 2:1 takes by weighing Graphene, join containing in the manganese compound solution that steps A obtains, fully stir, obtain mixed solution;
C, in step B, obtain mixed solution and dripping ammoniacal liquor, regulate pH to 8, and stirring reaction 1h, Mn obtained
3O
4/ Graphene mixed liquor;
D, the Mn that step C is obtained
3O
4/ Graphene mixed liquor reacts complete rear cooling at 150 ℃ of lower reaction 1h, obtains reactant liquor;
E, the reactant liquor that uses the method treatment step D of centrifugal, filtration or suction filtration to obtain, with solvent wash 3 times, drying obtains solid Mn with the precipitation that obtains
3O
4/ Graphene composite negative pole material;
F, take by weighing lithium-containing compound and titanium-containing compound by elemental lithium and titanium elements atomic ratio 3:5, then according to solid Mn
3O
4/ Graphene composite negative pole material and titanium-containing compound mass ratio 10:1 take by weighing solid Mn
3O
4/ Graphene composite negative pole material evenly mixes three kinds of solids, and adopts conventional high-energy ball milling to disperse, and obtains lithium-containing compound, titanium-containing compound and solid Mn
3O
4The solid mixture of/Graphene composite negative pole material;
G, get the solid mixture that obtains in the step F and put into heating furnace, the heating rate with 0.1 ℃/min under inert atmosphere rises to 600 ℃, and then heat treated 0.2h is cooled to room temperature under inert atmosphere, obtain Mn of the present invention
3O
4/ Graphene/lithium titanate nano composite anode material is lithium battery manganese base composite negative pole material.
Embodiment 7
A kind of preparation method of lithium battery manganese base composite negative pole material comprises following processing step:
A, will contain manganese compound and be dissolved in the solvent, be mixed with mass concentration and be 10% contain manganese compound solution;
B, by containing manganese compound and Graphene mass ratio 20:1 takes by weighing Graphene, join containing in the manganese compound solution that steps A obtains, fully stir, obtain mixed solution;
C, in step B, obtain mixed solution and dripping ammoniacal liquor, regulate pH to 10, and stirring reaction 5h, Mn obtained
3O
4/ Graphene mixed liquor;
D, the Mn that step C is obtained
3O
4/ Graphene mixed liquor reacts complete rear cooling at 200 ℃ of lower reaction 5h, obtains reactant liquor;
E, the reactant liquor that uses the method treatment step D of centrifugal, filtration or suction filtration to obtain, with solvent wash 5 times, drying obtains solid Mn with the precipitation that obtains
3O
4/ Graphene composite negative pole material;
F, take by weighing lithium-containing compound and titanium-containing compound by elemental lithium and titanium elements atomic ratio 5:5, then according to solid Mn
3O
4/ Graphene composite negative pole material and titanium-containing compound mass ratio 100:1 take by weighing solid Mn
3O
4/ Graphene composite negative pole material evenly mixes three kinds of solids, and adopts conventional high-energy ball milling to disperse, and obtains lithium-containing compound, titanium-containing compound and solid Mn
3O
4The solid mixture of/Graphene composite negative pole material;
G, get the solid mixture that obtains in the step F and put into heating furnace, the heating rate with 1 ℃/min under inert atmosphere rises to 1000 ℃, and then heat treated 5h is cooled to room temperature under inert atmosphere, obtain Mn of the present invention
3O
4/ Graphene/lithium titanate nano composite anode material is lithium battery manganese base composite negative pole material.
Embodiment 8
A kind of preparation method of lithium battery manganese base composite negative pole material comprises following processing step:
A, will contain manganese compound and be dissolved in the solvent, what be mixed with mass concentration and be 1-10% contains manganese compound solution;
B, by containing manganese compound and Graphene mass ratio 11:1 takes by weighing Graphene, join containing in the manganese compound solution that steps A obtains, fully stir, obtain mixed solution;
C, in step B, obtain mixed solution and dripping ammoniacal liquor, regulate pH to 9, and stirring reaction 3h, Mn obtained
3O
4/ Graphene mixed liquor;
D, the Mn that step C is obtained
3O
4/ Graphene mixed liquor reacts complete rear cooling at 175 ℃ of lower reaction 3h, obtains reactant liquor;
E, the reactant liquor that uses the method treatment step D of centrifugal, filtration or suction filtration to obtain, with solvent wash 4 times, drying obtains solid Mn with the precipitation that obtains
3O
4/ Graphene composite negative pole material;
F, take by weighing lithium-containing compound and titanium-containing compound by elemental lithium and titanium elements atomic ratio 4:5, then according to solid Mn
3O
4/ Graphene composite negative pole material and titanium-containing compound mass ratio 55:1 take by weighing solid Mn
3O
4/ Graphene composite negative pole material evenly mixes three kinds of solids, and adopts conventional high-energy ball milling to disperse, and obtains lithium-containing compound, titanium-containing compound and solid Mn
3O
4The solid mixture of/Graphene composite negative pole material;
G, get the solid mixture that obtains in the step F and put into heating furnace, the heating rate with 0.55 ℃/min under inert atmosphere rises to 800 ℃, and then heat treated 2.6h is cooled to room temperature under inert atmosphere, obtain Mn of the present invention
3O
4/ Graphene/lithium titanate nano composite anode material is lithium battery manganese base composite negative pole material.
Embodiment 9
A kind of preparation method of lithium battery manganese base composite negative pole material comprises following processing step:
A, will contain manganese compound and be dissolved in the solvent, be mixed with mass concentration and be 8% contain manganese compound solution;
B, by containing manganese compound and Graphene mass ratio 15:1 takes by weighing Graphene, join containing in the manganese compound solution that steps A obtains, fully stir, obtain mixed solution;
C, in step B, obtain mixed solution and dripping ammoniacal liquor, regulate pH to 9.5, and stirring reaction 4h, Mn obtained
3O
4/ Graphene mixed liquor;
D, the Mn that step C is obtained
3O
4/ Graphene mixed liquor reacts complete rear cooling at 190 ℃ of lower reaction 4h, obtains reactant liquor;
E, the reactant liquor that uses the method treatment step D of centrifugal, filtration or suction filtration to obtain, with solvent wash 4 times, drying obtains solid Mn with the precipitation that obtains
3O
4/ Graphene composite negative pole material;
F, take by weighing lithium-containing compound and titanium-containing compound by elemental lithium and titanium elements atomic ratio 4.5:5, then according to solid Mn
3O
4/ Graphene composite negative pole material and titanium-containing compound mass ratio 65:1 take by weighing solid Mn
3O
4/ Graphene composite negative pole material evenly mixes three kinds of solids, and adopts conventional high-energy ball milling to disperse, and obtains lithium-containing compound, titanium-containing compound and solid Mn
3O
4The solid mixture of/Graphene composite negative pole material;
G, get the solid mixture that obtains in the step F and put into heating furnace, the heating rate with 0.75 ℃/min under inert atmosphere rises to 950 ℃, and then heat treated 3.5h is cooled to room temperature under inert atmosphere, obtain Mn of the present invention
3O
4/ Graphene/lithium titanate nano composite anode material is lithium battery manganese base composite negative pole material.
Embodiment 10
On the basis of embodiment 6-9, preferred:
Solvent in steps A and step e is any one in water, ethanol, acetone, formic acid, n-hexane or the toluene.
Refer at 0 ℃ that in the stirring described in step B and the step C rotating speed is to stir under the 100r/min.
In step D, the described 1-5h that reacts under 150-200 ℃ refers to react in water heating kettle.
In step G, described heating furnace is rotary furnace.
In step G, described inert atmosphere is nitrogen atmosphere.
Embodiment 11
On the basis of embodiment 6-9, preferred:
Solvent in steps A and step e is any one in water, ethanol, acetone, formic acid, n-hexane or the toluene.
Refer at 80 ℃ that in the stirring described in step B and the step C rotating speed is to stir under the 1500r/min.
In step D, the described 1-5h that reacts under 150-200 ℃ refers to react in water heating kettle.
In step G, described heating furnace is rotary furnace.
In step G, described inert atmosphere is nitrogen atmosphere.
Embodiment 12
On the basis of embodiment 6-9, preferred:
Solvent in steps A and step e is any one in water, ethanol, acetone, formic acid, n-hexane or the toluene.
Refer at 40 ℃ that in the stirring described in step B and the step C rotating speed is to stir under the 800r/min.
In step D, the described 1-5h that reacts under 150-200 ℃ refers to react in water heating kettle.
In step G, described heating furnace is rotary furnace.
In step G, described inert atmosphere is nitrogen atmosphere.
Embodiment 13
On the basis of embodiment 6-9, preferred:
Solvent in steps A and step e is any one in water, ethanol, acetone, formic acid, n-hexane or the toluene.
Refer at 20 ℃ that in the stirring described in step B and the step C rotating speed is to stir under the 1000r/min.
In step D, the described 1-5h that reacts under 150-200 ℃ refers to react in water heating kettle.
In step G, described heating furnace is rotary furnace.
In step G, described inert atmosphere is nitrogen atmosphere.
Claims (10)
1. lithium battery manganese base composite negative pole material, it is characterized in that: described lithium battery manganese base composite negative pole material is the particulate of 20-200nm, described lithium battery manganese base composite negative pole material contains manganese compound for adopting, Graphene is made solid Mn
3O
4/ Graphene composite negative pole material, the Mn that makes with lithium-containing compound and titanium-containing compound again
3O
4/ Graphene/lithium titanate nano composite anode material, the described mass ratio that contains manganese compound and Graphene is 20:1-2:1, the elemental lithium in described lithium-containing compound and the titanium-containing compound and titanium elements atomic ratio are 3:5-5:5, described solid Mn
3O
4The mass ratio of/Graphene composite negative pole material and titanium-containing compound is 10:1-100:1.
2. a kind of lithium battery manganese base composite negative pole material according to claim 1, it is characterized in that: it is characterized in that: described lithium-containing compound is lithium carbonate.
3. a kind of lithium battery manganese base composite negative pole material according to claim 1, it is characterized in that: it is characterized in that: the particle diameter of described titanium-containing compound is 50nm.
4. a kind of lithium battery manganese base composite negative pole material preparation method according to claim 1 is characterized in that: comprise following processing step:
A, will contain manganese compound and be dissolved in the solvent, what be mixed with mass concentration and be 1-10% contains manganese compound solution;
B, by containing manganese compound and Graphene mass ratio 20:1-2:1 takes by weighing Graphene, join containing in the manganese compound solution that steps A obtains, fully stir, obtain mixed solution;
C, in step B, obtain mixed solution and dripping ammoniacal liquor, regulate pH to 8-10, and stirring reaction 1-5h, Mn obtained
3O
4/ Graphene mixed liquor;
D, the Mn that step C is obtained
3O
4/ Graphene mixed liquor reacts complete rear cooling at 150-200 ℃ of lower reaction 1-5h, obtains reactant liquor;
E, the reactant liquor that uses the method treatment step D of centrifugal, filtration or suction filtration to obtain, with solvent wash 3-5 time, drying obtains solid Mn with the precipitation that obtains
3O
4/ Graphene composite negative pole material;
F, take by weighing lithium-containing compound and titanium-containing compound by elemental lithium and titanium elements atomic ratio 3:5-5:5, then according to solid Mn
3O
4/ Graphene composite negative pole material and titanium-containing compound mass ratio 10:1-100:1 take by weighing solid Mn
3O
4/ Graphene composite negative pole material evenly mixes three kinds of solids, and adopts conventional high-energy ball milling to disperse, and obtains lithium-containing compound, titanium-containing compound and solid Mn
3O
4The solid mixture of/Graphene composite negative pole material;
G, get the solid mixture that obtains in the step F and put into heating furnace, the heating rate with 0.1-1 ℃/min under inert atmosphere rises to 600-1000 ℃, and then heat treated 0.2-5h is cooled to room temperature under inert atmosphere, obtain Mn of the present invention
3O
4/ Graphene/lithium titanate nano composite anode material is lithium battery manganese base composite negative pole material.
5. a kind of lithium battery manganese base composite negative pole material preparation method according to claim 4, it is characterized in that: the solvent in steps A and step e is any one in water, ethanol, acetone, formic acid, n-hexane or the toluene.
6. a kind of lithium battery manganese base composite negative pole material preparation method according to claim 4 is characterized in that: refer at 0-80 ℃ that in the stirring described in step B and the step C rotating speed is to stir under the 100-1500r/min.
7. a kind of lithium battery manganese base composite negative pole material preparation method according to claim 4 is characterized in that: in step D, describedly refer to react in water heating kettle at 150-200 ℃ of lower reaction 1-5h.
8. a kind of lithium battery manganese base composite negative pole material preparation method according to claim 4, it is characterized in that: in step G, described heating furnace is rotary furnace.
9. a kind of lithium battery manganese base composite negative pole material preparation method according to claim 4, it is characterized in that: in step G, described inert atmosphere is nitrogen atmosphere.
10. lithium battery that adopts the lithium battery manganese base composite negative pole material described in the claim 1 to make.
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| CN109148894A (en) * | 2018-09-05 | 2019-01-04 | 天津瑞晟晖能科技有限公司 | Lithium ion cell positive, all-solid lithium-ion battery and preparation method thereof and electricity consumption device |
| CN109148821A (en) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | A kind of high-capacity lithium ion battery primary battery anode composite preparation method |
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