CN103811738A - Novel titanate capable being used as lithium ion secondary battery cathode material - Google Patents
Novel titanate capable being used as lithium ion secondary battery cathode material Download PDFInfo
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- CN103811738A CN103811738A CN201210458249.8A CN201210458249A CN103811738A CN 103811738 A CN103811738 A CN 103811738A CN 201210458249 A CN201210458249 A CN 201210458249A CN 103811738 A CN103811738 A CN 103811738A
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- lithium
- negative material
- strontium
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract 2
- 239000010406 cathode material Substances 0.000 title description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000011160 research Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000003438 strontium compounds Chemical class 0.000 claims description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910010711 Li2+xSrmM1-mTi5+nN1-nO14-y Inorganic materials 0.000 abstract 1
- 239000006182 cathode active material Substances 0.000 abstract 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 229910052712 strontium Inorganic materials 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a novel titanate capable of being used as a lithium ion secondary battery cathode active material. The general formula of the active material is Li2+xSrmM1-mTi5+nN1-nO14-y, wherein M is one or the combination selected from Al, Ba, Ca, Ce, Cs, La, Mg, K, Na, Sr, Mn and Sn, N is one or the combination selected from Mn, Ti, Co, Zr and V, x is greater than or equal to 0 and is less than or equal to 0.5, m is greater than or equal to 0 and is less than or equal to 1, n is greater than or equal to 0 and less than or equal to 1, and y is greater than or equal to 0 and is less than or equal to 1. The Li+/Li operating voltage from the material is 0.8-1.45V, and the metal Li potential is low compared with a lithium titanate material; when the novel titanate is paired with lithium manganate or cobalt acid lithium, the operation voltage higher than that of a battery taking lithium titanate as a negative electrode is obtained, and the safety problem of battery short circuit due to formation of lithium dendrites caused by separation of lithium metal is solved.
Description
Technical field
The present invention relates to clean energy resource field, a kind of Novel Titanium hydrochlorate that can be used as active material for negative pole of Li-ion secondary battery and preparation method thereof is provided.
Background technology
The aggravation of the environmental problem of bringing along with energy crisis and use " fossil fuel "; secondary lithium battery is as a kind of new cleaning fuel; obtain the concern of increasing research institution and new forms of energy enterprise, national governments also strengthen the supporting dynamics to these battery research and development one after another.
At present, the range of application of secondary lithium battery is more and more wider, has successfully been applied to the fields such as mobile phone, notebook computer, electric automobile and energy storage project.Along with the check of the deep and practical application of researching and developing, graphite cathode class secondary lithium battery has also spilt cruelly a series of safety problems such as " Li dendrite " (referring to Patent Document 1CN200810141740.1).People wish to find a kind of material that can substitute graphite cathode, to avoid separating out the problem of Li dendrite.The Novel lithium secondary battery cathode material that spinel type lithium titanate has " zero strain " and long-life characteristics as one has caused people's extensive concern, it is that 1.55V(refers to Patent Document 2CN200710122074.2 to Li+/Li workbench voltage), higher than the deposition potential of lithium metal.Negative electrode active material with lithium titanate as lithium secondary battery, can successfully avoid separating out and form the potential safety hazard that Li dendrite causes, the fail safe that has improved battery due to lithium metal.
But, because lithium titanate self current potential is high, cause the full cell voltage that makes negative pole of it to decline, the battery applications scope that obtains is little, be not suitable for large-scale industry uses.
Summary of the invention
In order to overcome the Li dendrite of graphite cathode, utilize " zero strain " and the long-life characteristics of lithium titanate, avoid the problems such as the complete battery operated voltage of the high impact of negative pole self current potential simultaneously.The present invention proposes a kind of Novel Titanium hydrochlorate as lithium secondary battery cathode material.
For addressing the above problem, the technical scheme of Novel Titanium hydrochlorate of ion secondary battery cathode material lithium of the present invention and preparation method thereof is specific as follows:
A kind of lithium rechargeable battery active material, it has following general formula:
Li
2+xSr
mM
1-mTi
5+nN
1-nO
14-y，
Wherein, M is one or more the combination in Al, Ba, Ca, Ce, Cs, La, Lr, Mg, K, Na, Mn or Sn, and N is one or more the combination in Mn, Co, Zr or V, 0≤x≤0.5,0≤m≤1,0≤n≤1,0≤y≤1.
This material its to Li
+/ Li working voltage platform scope is 0.8 ~ 1.45V; Its crystal is rhombic system.
Preferably, y=0, n=1; Now in material, Sr is replaced by M part, and general formula becomes Li
2+xsr
mm
1-mti
6o
14, wherein M is one or more the combination in Al, Ba, Ca, Ce, Cs, La, Mg, K, Na, Mn or Sn, 0≤x≤0.5,0≤m≤1.
Another preferred version of the present invention is: y=0, m=1; Now, in material, Ti is replaced by N part, and general formula is Li
2+xsrTi
5+nn
1-no
14, wherein N is one or more the combination in Mn, Co, Zr or V, 0≤x≤0.5,0≤n≤1.
Preferred again, n=1, m=1; Material makes under inertia or reducing atmosphere, has general formula Li
2+xsrTi
6o
14-y, wherein inert atmosphere is N
2, Ar or its mixed atmosphere, reducing atmosphere is for containing H
2or NH
3with the gaseous mixture of inert atmosphere, 0≤x≤0.5,0≤y≤1.
In such scheme, described negative material surface can be coated with conducting metal, metal oxide or conductive carbon agent.Wherein conducting metal and metal oxide are one or more the combination in Sn, Cu, Ag or Al and their oxide, conductive carbon agent is the carbon simple substance such as graphite, Graphene, carbon nano-tube, or one or more of the Organic Compounds RESEARCH OF PYROCARBON under inertia or reducing atmosphere, or several combinations in described carbon simple substance and described RESEARCH OF PYROCARBON.
The preparation method of Novel Titanium hydrochlorate of the present invention comprises the following steps:
1) take needed raw material by each metallic element mol ratio in product, mix and be placed in atmosphere furnace, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours;
2) said mixture is naturally cooled to room temperature, grind, then gained powder is placed in to atmosphere furnace and is warmed up to 1000 ℃ of insulation 24h, naturally cool to room temperature and can obtain product.
Wherein, raw material is the compound of lithium compound, titanium compound, strontium compound and metallic element M, N.
Described lithium compound is one or more the combination in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium borate or lithium chloride;
Described titanium compound is rutile titanium dioxide or anatase titanium dioxide;
Described strontium compound is one or more the combination in strontium hydroxide, strontium carbonate, strontium chloride, strontium acetate or strontium sulfate;
The compound of described metallic element M, N is one or more the combination in oxide, carbonate or the hydroxide of respective metal element.
Take above-mentioned titanate as anodal, the button cell working voltage platform scope of making take lithium metal as negative pole is 0.8～1.45V, and this value is higher than the deposition potential of lithium metal, lower than Li
4ti
5o
12(vs.Li
+/ Li) 1.55V platform.
Novel Titanium silicate material of the present invention is to Li
+/ Li operating voltage is 0.8～1.45V, compared with lithium titanate material, lower to metal Li current potential, like this when with LiMn2O4 or the pairing of cobalt acid lithium, can obtain and compare the operating voltage that the battery take lithium titanate as negative pole is higher, and can solve equally and separate out and form due to lithium metal the safety problem that Li dendrite causes battery short circuit.This material high rate performance is better, and specific area is little, embodies good processing characteristics in battery manufacturing process, and in addition, its synthesis technique is simple, and raw material cheapness is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the Novel Titanium hydrochlorate XRD spectra of the embodiment of the present invention 1;
Fig. 2 is Novel Titanium hydrochlorate electron microscope (SEM) photo of the embodiment of the present invention 1;
Fig. 3 is that the Novel Titanium hydrochlorate of the embodiment of the present invention 1 is to Li
+charging/discharging voltage-specific capacity curve of/Li.
Embodiment
Titanate the present invention being proposed below in conjunction with embodiment is described in more detail.And protection scope of the present invention is not only confined to following examples.The those of ordinary skill of described technical field, according to above disclosure of the present invention, all can be realized object of the present invention.
Embodiment mono-:
Li
2.1srTi
6o
14preparation
Selecting lithium carbonate, anatase titanium dioxide and strontium carbonate is raw material, Li:Sr:Ti=2.1:1:6 batching in molar ratio, be placed in atmosphere furnace through mixing, under air atmosphere, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours, then naturally cool to room temperature, after grinding, then powder is placed in to atmosphere furnace, and under air atmosphere, be warmed up to 1000 ℃ of insulation 24h, naturally cool to afterwards room temperature and can obtain faint yellow product.Fig. 1 is its X-ray diffraction collection of illustrative plates, and figure bis-is its ESEM (SEM) photo, and it is Fig. 3 to charging/discharging voltage-capacity curve of Li+/Li.
Embodiment bis-:
Li
2.1srTi
6o
14preparation
Selecting lithium carbonate, anatase titanium dioxide and strontium hydroxide is raw material, Li:Sr:Ti=2.1:1:6 batching in molar ratio, be placed in atmosphere furnace through mixing, under air atmosphere, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours, then naturally cool to room temperature, after grinding, then powder is placed in to atmosphere furnace, and under air atmosphere, be warmed up to 1000 ℃ of insulation 24h, naturally cool to afterwards room temperature and can obtain faint yellow product.
Embodiment tri-:
Li
2.1sr
0.98mg
0.02ti
6o
14preparation
Selecting lithium carbonate, anatase titanium dioxide, strontium carbonate and magnesium hydroxide is raw material, Li:Sr:Mg:Ti=2.1:0.98:0.02:6 batching in molar ratio, be placed in atmosphere furnace through mixing, under air atmosphere, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours, then naturally cool to room temperature, after grinding, then powder is placed in to atmosphere furnace, and under air atmosphere, be warmed up to 1000 ℃ of insulation 24h, naturally cool to afterwards room temperature and can obtain faint yellow product.
Embodiment tetra-:
Li
2.1srTi
5.98mn
0.02o
14preparation
Selecting lithium carbonate, anatase titanium dioxide, strontium carbonate and manganese dioxide is raw material, Li:Sr:Ti:Mn=2.1:1:5.98:0.02 batching in molar ratio, be placed in atmosphere furnace through mixing, under air atmosphere, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours, then naturally cool to room temperature, after grinding, then powder is placed in to atmosphere furnace, and under air atmosphere, be warmed up to 1000 ℃ of insulation 24h, naturally cool to afterwards room temperature and can obtain faint yellow product.
Embodiment five:
Li
2.1srTi
6o
13.98preparation
Selecting lithium carbonate, anatase titanium dioxide and strontium carbonate is raw material, and Li:Sr:Ti=2.1:1:6 batching in molar ratio, is placed in atmosphere furnace through mixing, and logical reducibility gas (is N
2with H
2gaseous mixture, volume ratio N
2: H
2=95:5) prepurging to oxygen content in stove is less than after 100ppm, regulating reducibility gas flow is 3L/min, and be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours, then naturally cool to room temperature, after grinding, then powder is placed in to atmosphere furnace, under reducing atmosphere, be warmed up to 1000 ℃ of insulation 24h, naturally cool to afterwards room temperature and can obtain faint yellow product.
Embodiment six:
Carbon is coated Li
2.1srTi
6o
14preparation
Selecting lithium carbonate, anatase titanium dioxide, strontium carbonate and glucose is raw material, Li:Sr:Ti in molar ratio: glucose=2.1:1:6:0.45 batching, be placed in atmosphere furnace through mixing, logical nitrogen prepurging to oxygen content in stove is less than after 100ppm, adjusting mixed gas flow is 3L/min, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours, then naturally cool to room temperature, after grinding, again powder is placed in to atmosphere furnace, under nitrogen atmosphere, is warmed up to 1000 ℃ of insulation 24h, naturally cool to afterwards room temperature and can obtain grey black carbon coated product.
Claims (13)
1. a negative material for lithium rechargeable battery, is characterized in that this material has following general formula:
Li
2+xSr
mM
1-mTi
5+nN
1-nO
14-y，
Wherein, M is one or more in Al, Ba, Ca, Ce, Cs, La, Mg, K, Na, Mn or Sn, and N is one or more in Mn, Co, Zr or V, 0≤x≤0.5,0≤m≤1,0≤n≤1,0≤y≤1.
2. negative material as described in claim 1, is characterized in that Li
+/ Li voltage platform is 0.8～1.45V.
3. negative material as described in claim 1, the crystal structure that it is characterized in that this material is rhombic system.
4. negative material as described in claim 1, is characterized in that preferred y=0 in described general formula, n=1.
5. negative material as described in claim 1, it is characterized in that preferred, y=0 in general formula, m=1.
6. negative material as described in claim 1, it is characterized in that preferred, n=1 in general formula, when m=1, described negative material makes under inertia or reducing atmosphere, wherein inert atmosphere is N
2, Ar or its mixed atmosphere, reducing atmosphere is for containing H
2or NH
3gaseous mixture with inert atmosphere.
7. negative material as described in claim 1, it is characterized in that described negative material surface is coated with conducting metal, metal oxide or conductive carbon agent, wherein conducting metal and metal oxide are one or more the combination in Sn, Cu, Ag, Al and oxide thereof, conductive carbon agent is the carbon simple substance such as graphite, Graphene, carbon nano-tube, or one or more of the Organic Compounds RESEARCH OF PYROCARBON under inertia or reducing atmosphere, or several combinations in described carbon simple substance and described RESEARCH OF PYROCARBON.
8. the preparation method of the negative material as described in above arbitrary claim, is characterized in that comprising the steps:
1) take needed raw material by each metallic element mol ratio in product, mix and be placed in atmosphere furnace, be raised to 700 degree with 5 ℃/min programming rate, be incubated 8 hours;
2) said mixture is naturally cooled to room temperature, grind, then gained powder is placed in to atmosphere furnace and is warmed up to 1000 ℃ of insulation 24h, naturally cool to room temperature and can obtain product.
9. the preparation method described in claim 8, is characterized in that raw material described in step 1) is the compound of lithium compound, titanium compound, strontium compound and metallic element M, N.
10. the preparation method described in claim 9, is characterized in that described lithium compound is one or more the combination in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium borate or lithium chloride.
Preparation method described in 11. claims 9, is characterized in that described titanium compound is the one in rutile titanium dioxide or anatase titanium dioxide.
Preparation method described in 12. claims 9, is characterized in that described strontium compound is one or more the combination in strontium hydroxide, strontium carbonate, strontium chloride, strontium acetate or strontium sulfate.
Preparation method described in 13. claims 9, the compound that it is characterized in that described metallic element M, N is one or more the combination in the oxide, carbonate, hydroxide of respective metal element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210458249.8A CN103811738A (en) | 2012-11-14 | 2012-11-14 | Novel titanate capable being used as lithium ion secondary battery cathode material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185972A (en) * | 2014-05-27 | 2015-12-23 | 中信国安盟固利动力科技有限公司 | Composite titanate negative electrode material of lithium ion secondary battery and synthetic method thereof |
| CN105417576A (en) * | 2014-09-23 | 2016-03-23 | 中信国安盟固利动力科技有限公司 | Preparation method for high power spherical titanate anode material |
| CN106033809A (en) * | 2015-03-17 | 2016-10-19 | 中信国安盟固利动力科技有限公司 | Composite titanium oxide negative electrode material and fast charging type lithium ion battery containing the same |
| CN106104866A (en) * | 2015-01-30 | 2016-11-09 | 株式会社东芝 | Battery component and set of cells |
| EP3136473A1 (en) * | 2015-08-25 | 2017-03-01 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery module, battery pack, automobile and vehicle |
| CN106575754A (en) * | 2014-12-02 | 2017-04-19 | 株式会社东芝 | Negative electrode active material, nonaqueous electrolyte battery and battery pack |
| EP3220457A1 (en) * | 2016-03-15 | 2017-09-20 | Kabushiki Kaisha Toshiba | Electrode active material, non-aqueous electrolyte secondary battery, battery pack, and vehicle |
| US10505186B2 (en) | 2015-01-30 | 2019-12-10 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
| US10516163B2 (en) | 2015-03-13 | 2019-12-24 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131941A1 (en) * | 2002-12-19 | 2004-07-08 | The University Of Chicago | Anode material for lithium batteries |
| JP2005267940A (en) * | 2004-03-17 | 2005-09-29 | Toshiba Corp | Nonaqueous electrolyte battery |
| US20060263291A1 (en) * | 2004-11-23 | 2006-11-23 | Carmine Torardi | Mesoporous amorphous oxide of titanium |
| CN102237523A (en) * | 2010-05-06 | 2011-11-09 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery and rechargeable lithium battery including same |
| WO2012002365A1 (en) * | 2010-06-30 | 2012-01-05 | 株式会社 村田製作所 | Electrode active material, method for producing same, and nonaqueous electrolyte secondary battery comprising same |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
-
2012
- 2012-11-14 CN CN201210458249.8A patent/CN103811738A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131941A1 (en) * | 2002-12-19 | 2004-07-08 | The University Of Chicago | Anode material for lithium batteries |
| JP2005267940A (en) * | 2004-03-17 | 2005-09-29 | Toshiba Corp | Nonaqueous electrolyte battery |
| US20060263291A1 (en) * | 2004-11-23 | 2006-11-23 | Carmine Torardi | Mesoporous amorphous oxide of titanium |
| CN102237523A (en) * | 2010-05-06 | 2011-11-09 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery and rechargeable lithium battery including same |
| WO2012002365A1 (en) * | 2010-06-30 | 2012-01-05 | 株式会社 村田製作所 | Electrode active material, method for producing same, and nonaqueous electrolyte secondary battery comprising same |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185972B (en) * | 2014-05-27 | 2018-05-29 | 中信国安盟固利动力科技有限公司 | The compound titanate negative material and its synthetic method of a kind of lithium rechargeable battery |
| CN105185972A (en) * | 2014-05-27 | 2015-12-23 | 中信国安盟固利动力科技有限公司 | Composite titanate negative electrode material of lithium ion secondary battery and synthetic method thereof |
| CN105417576A (en) * | 2014-09-23 | 2016-03-23 | 中信国安盟固利动力科技有限公司 | Preparation method for high power spherical titanate anode material |
| CN105417576B (en) * | 2014-09-23 | 2017-05-03 | 中信国安盟固利动力科技有限公司 | Preparation method for high power spherical titanate anode material |
| CN106575754A (en) * | 2014-12-02 | 2017-04-19 | 株式会社东芝 | Negative electrode active material, nonaqueous electrolyte battery and battery pack |
| EP3229296A4 (en) * | 2014-12-02 | 2018-07-18 | Kabushiki Kaisha Toshiba | Negative electrode active material, nonaqueous electrolyte battery and battery pack |
| US10553868B2 (en) | 2014-12-02 | 2020-02-04 | Kabushiki Kaisha Toshiba | Negative electrode active material, nonaqueous electrolyte battery, battery pack and vehicle |
| CN106104866B (en) * | 2015-01-30 | 2020-01-21 | 株式会社东芝 | Battery pack and battery pack |
| US10511014B2 (en) | 2015-01-30 | 2019-12-17 | Kabushiki Kaisha Toshiba | Battery module and battery pack |
| CN106104866A (en) * | 2015-01-30 | 2016-11-09 | 株式会社东芝 | Battery component and set of cells |
| US10505186B2 (en) | 2015-01-30 | 2019-12-10 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
| US10516163B2 (en) | 2015-03-13 | 2019-12-24 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
| CN106033809B (en) * | 2015-03-17 | 2018-10-16 | 中信国安盟固利动力科技有限公司 | A kind of composite titanium system oxide cathode material and the fast charging type lithium ion battery containing it |
| CN106033809A (en) * | 2015-03-17 | 2016-10-19 | 中信国安盟固利动力科技有限公司 | Composite titanium oxide negative electrode material and fast charging type lithium ion battery containing the same |
| JP2017045569A (en) * | 2015-08-25 | 2017-03-02 | 株式会社東芝 | Active material for battery, non-aqueous electrolyte battery, assembly battery, battery pack and vehicle |
| US10096828B2 (en) | 2015-08-25 | 2018-10-09 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery module, battery pack, automobile and vehicle |
| CN106486655B (en) * | 2015-08-25 | 2019-06-28 | 株式会社东芝 | Active material, nonaqueous electrolyte battery, group battery, battery pack, automobile and vehicle |
| CN106486655A (en) * | 2015-08-25 | 2017-03-08 | 株式会社东芝 | Active substance, nonaqueous electrolyte battery, Battery pack, battery bag, automobile and vehicle |
| EP3136473A1 (en) * | 2015-08-25 | 2017-03-01 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery module, battery pack, automobile and vehicle |
| US10020505B2 (en) | 2016-03-15 | 2018-07-10 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack, and vehicle |
| JP2017168264A (en) * | 2016-03-15 | 2017-09-21 | 株式会社東芝 | Active material, nonaqueous electrolyte battery, battery pack, and motor vehicle |
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