CN102522535B - 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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- CN102522535B CN102522535B CN201110421634.0A CN201110421634A CN102522535B CN 102522535 B CN102522535 B CN 102522535B CN 201110421634 A CN201110421634 A CN 201110421634A CN 102522535 B CN102522535 B CN 102522535B
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- ion battery
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- lithium titanate
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000010406 cathode material Substances 0.000 title abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 124
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 82
- 239000010936 titanium Substances 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 230000002441 reversible effect Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 235000011194 food seasoning agent Nutrition 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229920005546 furfural resin Polymers 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
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 23
- 238000007599 discharging Methods 0.000 abstract description 13
- 229910012465 LiTi Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 235000010215 titanium dioxide Nutrition 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000007580 dry-mixing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 2
- -1 anatase titanium dioxides Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
- 229910004796 P—Li Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method thereof. The lithium ion battery cathode material is a lithium titanate with a controllable valence state, the lithium titanate is expressed by a chemical formula of LiTi(IV)5-xTi(III)xO(12-x/2), wherein x is larger than 0 while smaller than 5; and IV and III respectively refer to valence states of Ti. The lithium titanate with controllable valence state is of a spinelle structure, the outline thereof is blue, and the lithium titanate has good conductivity, the inherent conductivity thereof is 10-3-10-8 S/cm, and the lithium embedding potential thereof is smaller than 1.55 V(vs Li/Li+). The preparation method comprises the steps of: 1) uniformly blending the raw materials; 2) performing a solid phase reaction; 3) pre-treating; and 4) sintering the solid phase. The lithium ion battery prepared by the cathode material of the invention has a high voltage, excellent multiplying power charging and discharging properties and a high energy density.
Description
[technical field]
The present invention relates to new energy materials technical field, particularly relate to a kind of lithium ion battery cathode material and its preparation method.
[background technology]
Increasingly serious along with energy crisis, readjusts the energy structure extremely urgent.People, on the one hand by tapping a new source of energy to meet ever-increasing demand, select rationally to utilize regenerative resource on the other hand.In the process of exploitation regenerative resource, electrical power storage technology plays an important role.For solving the harmonious problem of electric power system appearance in electrical production and consumption and meeting the grid-connected needs of new forms of energy electric power that the fluctuation such as wind-powered electricity generation, photovoltaic generation is stronger, extensive energy-accumulating power station is ready to appear.The chemical power source that can be used at present energy storage field mainly contains lead-acid battery, sodium-sulphur battery, flow battery and lithium ion battery.Wherein, lead-acid battery stable performance, but the life-span is too short, and energy density is too small; Sodium-sulphur battery must ensure the working temperature of 300 DEG C; Flow battery energy density is too low.Lithium ion battery is because of its excellent combination property, and becomes the emphasis of research.Meanwhile, lithium ion battery also becomes the power source of electric automobile and the tool potentiality of hybrid vehicle because having energy density high.After vehicle-mounted lithium ion battery market occurred in 2009, the application of lithium ion battery in electric automobile become trend, and Ge great state all furnishes a huge amount of money for to help, and for China, is taken as especially the hope of automobile industry " bend is overtaken other vehicles ".The development of electric automobile will be that far-reaching chance is carried out in lithium ion battery industrial zone, the foreseeable future, the electrokinetic cell market of lithium ion battery will surmount its at consumption electricity the existing market in product.
Lithium titanate, as lithium ion battery negative material, can avoid carbon negative pole material surface to form the special capacity fade that solid electrolyte film and Li dendrite and lithium ion battery cause due to change in volume in cyclic process.The These characteristics of lithium titanate has ensured security performance and the cycle life that lithium titanate lithium ion battery is high.In addition, in lithium titanate, lithium ion has three-dimensional netted diffusion admittance, and its chemical diffusion coefficient is about 2 × 10
-8cm
2/ s, almost than the high order of magnitude of graphite, is applicable to fast charging and discharging.Therefore, the lithium ion battery using lithium titanate as negative material is expected to be applied in large-scale energy-accumulating power station and Vehicular dynamic battery.
Although lithium titanate has the advantage of highly significant for lithium-ion-power cell and extensive energy-storage battery, but some problems that lithium titanate exists at present have seriously hindered its Commercialization application process: 1) conductance of lithium titanate is low, because its intrinsic conductivity is 10
-9s/cm, makes it present the feature of insulator.In the time of high current charge-discharge, the electronics of its enrichment by by polarity effect conversely limiting lithium ion insertion and deviate from, and make material electrochemical performance worsen.2) the high removal lithium embedded current potential of lithium titanate brings low-voltage (the 1.55V vs Li of battery
+/ Li), the only about 2.2V～2.5V of lithium ion battery voltage of the preparation that matches with the conventional positive electrode such as cobalt acid lithium, LiMn2O4, than the low about 1.5V of the lithium ion battery using graphite as negative material left and right.Therefore how to improve the conductivity of lithium titanate and reduce its lithium removal lithium embedded current potential and become the important topic of improving lithium titanate performance.
[summary of the invention]
The present invention is intended to address the above problem, and provides a kind of voltage high, and fail safe is good, has good rate charge-discharge performance and the lithium ion battery negative material of high-energy-density more.
The present invention also aims to provide a kind of preparation method of described lithium ion battery negative material.
For achieving the above object, the invention provides a kind of lithium ion battery negative material, this lithium ion battery negative material is controlled valence state lithium titanate, and its chemical formula is: Li
4ti (IV)
5-xti (III)
xo
(12-x/2), wherein, 0 < x < 5; IV, III are respectively the valence state of Ti, and this lithium ion battery negative material structure is spinel structure.
The intrinsic conductivity of this lithium ion battery negative material is 10
-3～10
-8s/cm.
The embedding lithium current potential of this lithium ion battery negative material is lower than the lithium titanate Li of stoichiometric proportion
4ti
5o
12embedding lithium current potential.
The embedding lithium current potential of this lithium ion battery negative material is 1.50～1.55V.
The reversible specific capacity of this lithium ion battery negative material is 120mAh/g～170mAh/g, can realize 1～20C rate charge-discharge.
The appearance color of this lithium ion battery negative material is blue.
The present invention also provides the preparation method of described lithium ion battery negative material, and the method comprises the steps:
A, by He Tai source, lithium source by lithium, titanium mol ratio Li: Ti=0.80～0.84: 1 mixes;
B, the mixture in Yu Tai source, lithium source is warming up to 600～1000 DEG C with the programming rate of 1～50 DEG C/min in high temperature furnace, constant temperature 3～72 hours, cools to room temperature with the furnace, obtains the lithium titanate pure phase of stoichiometric proportion;
C, lithium titanate pure phase is first added to percentage by weight is the solvent that 0.5～10 additive and percentage by weight are 100～900%, grind or Ultrafine Grinding carries out ball milling mixing by stirring, and be dried by heating evaporation seasoning, vacuum and heating drying method or spray drying process, described additive is one or more in glucose, sucrose, starch, polyvinyl alcohol, phenolic resins, epoxy resin and furfural resin, and described solvent is deionized water, ethanol or acetone;
D, will be dried after material put into high temperature furnace, under inert protective gas, be warming up to 600～900 DEG C with the programming rate of 1～50 DEG C/min, constant temperature 2～30 hours, after abundant reaction, is cooled to room temperature, obtains controlled valence state lithium titanate.
Described lithium source is lithium carbonate, lithium hydroxide or lithium nitrate, and titanium source is the titanium dioxide of anatase, rutile, amorphous or brookite type.
Preferably, in step b, the mixture in Yu Tai source, lithium source is warming up to 700～850 DEG C with the programming rate of 5～20 DEG C/min in high temperature furnace, constant temperature 12～48 hours, cools to room temperature with the furnace, obtains the lithium titanate pure phase of stoichiometric proportion; In steps d, after being dried, material is put into high temperature furnace, under inert protective gas, is warming up to 600～750 DEG C with the programming rate of 5～20 DEG C/min, and constant temperature 6～24 hours, after abundant reaction, is cooled to room temperature, obtains controlled valence state lithium titanate.
Preferably, in step c, it is the solvent that 1～7.5 additive and percentage by weight are 200～300 that lithium titanate pure phase is first added to percentage by weight, grind or Ultrafine Grinding carries out ball milling mixing by stirring, and be dried by heating evaporation seasoning, vacuum and heating drying method or spray drying process, described additive is one or more in glucose, sucrose, starch, polyvinyl alcohol, phenolic resins, epoxy resin and furfural resin, and described solvent is deionized water, ethanol or acetone.
Contribution of the present invention is, it provides a kind of lithium ion battery negative material of new construction.This negative material is charging and discharging in process, and compared with the charging and discharging curve of its charging and discharging curve and the lithium titanate of stoichiometric proportion, its current potential is offset to electronegative potential; Controlled valence state lithium titanate has better conductivity simultaneously, even if also can meet the charge/discharge capacity of actual application level in the situation that not adding conductive agent.It is high that the lithium ion battery of negative material assembling of the present invention has voltage, and fail safe is good, the features such as good rate charge-discharge performance and more high-energy-density.
[brief description of the drawings]
Lithium titanate (being white in color) the contrast photograph of Fig. 1 stoichiometric proportion that to be the controlled valence state lithium titanate prepared of embodiments of the invention 1, embodiment 2 (being blue) prepare with comparative example 1.
Fig. 2 is the XRD collection of illustrative plates of the controlled valence state lithium titanate prepared of embodiments of the invention 1.
The XPS collection of illustrative plates of the lithium titanate (White LTO in figure) of Fig. 3 stoichiometric proportion that to be the controlled valence state lithium titanate (Blue LTO in figure) prepared of embodiments of the invention 1 prepare with comparative example 1.
The lithium titanate (White LTO in figure) of Fig. 4 stoichiometric proportion that to be the controlled valence state lithium titanate (Blue LTO in figure) prepared of embodiments of the invention 1 prepare with comparative example 1 at the charging and discharging curve figure not adding under button half-cell 0.2C and the 1C multiplying power electric current being assembled under the condition of conductive agent.
The lithium titanate (White LTO in figure) of Fig. 5 stoichiometric proportion that to be the controlled valence state lithium titanate (Blue LTO in figure) prepared of embodiments of the invention 1 prepare with comparative example 1 is at the charging and discharging curve figure adding under button half-cell 0.2C and the 1C multiplying power electric current being assembled under the condition of conductive agent.
Fig. 6 is that (lithium titanate of the stoichiometric proportion of a) preparing with comparative example 1 in figure (b) is adding the powerful charging and discharging curve figure of button half-cell being assembled under the condition of conductive agent in figure to the controlled valence state lithium titanate prepared of embodiments of the invention 1.
[embodiment]
The following example is further explanation of the present invention, and the present invention is not constituted any limitation.
In order to test the chemical property that adopts lithium ion battery negative material provided by the invention, by controlled the lithium ion battery negative material in the present invention valence state lithium titanate (LTO) and binding agent Kynoar (PVDF), conductive agent Super P-Li (SP), solvent 1-METHYLPYRROLIDONE (NMP) by LTO: PVDF: SP: NMP=80: 10: 10: 80 or 90: 10: 0: 80 mass ratio is uniformly mixed and is prepared into slurry, be coated in aluminium foil surface, make negative pole, taking metal lithium sheet as to electrode, be prepared into button half-cell, test.Charging/discharging voltage scope 0.8V～2.5V.
Embodiment 1
By lithium, titanium mol ratio Li: Ti=0.80: 1 takes He Tai source, lithium source.Lithium source in the present embodiment is lithium carbonate, gets 14.78 parts of lithium carbonates.Titanium source is anatase titanium dioxide, gets 39.94 parts of anatase titanium dioxides.The He Tai source, lithium source taking is mixed mutually.He Tai source, mixed lithium source is placed in the high temperature furnace that is connected with air and rises to 700 DEG C with the programming rate of 1 DEG C/min, carry out sintering.After constant temperature 48 hours, cool to room temperature with the furnace.The product that sintering obtains is spinel structure stoichiometric proportion lithium titanate.
Then in the material obtaining after sintering, add additive and solvent.Additive in the present embodiment is glucose, and glucose accounts for 5% (mass percent, lower same) of sintering resulting materials.In the present embodiment, described solvent is deionized water, and to add ionized water to make solid content be 20%.This additive can be by the titanic in sintering resulting materials, is partly reduced to titanous at sintering for the second time.
Above-mentioned mixed liquor is joined in Ultrafine Grinding, and ball milling 10 hours, fully mixes and reacts.The time of ball milling also can optionally change, as long as the material in mixed liquor fully mixes and is ground to certain size.Ball milling fully can be controlled the grain size of follow-up product, makes lithium ion battery negative material of the present invention have outstanding rate charge-discharge performance.
Then above-mentioned material is dried.Dry method can be heating evaporation seasoning, vacuum and heating drying method or spray drying process etc.Dry for spraying in the present embodiment.
The material obtaining is risen to 600 DEG C with the programming rate of 10 DEG C/min in the high temperature furnace that is connected with high-purity argon gas, carry out double sintering, constant temperature, after 6 hours, cools to room temperature with the furnace.After being cooled to room temperature, resulting materials is lithium ion battery negative material of the present invention, and this negative material is controlled valence state lithium titanate, and concrete product is as shown in a container in Fig. 1, and it is blue that this lithium ion battery negative material outward appearance is.After testing, the controlled valence state lithium titanate of this lithium ion battery negative material can be by following chemical formulation:
Li
4Ti(IV)
5-xTi(III)
xO
(12-x/2)
Wherein, 0 < x < 5; IV, III are respectively the valence state of Ti.
Fig. 2 is the XRD collection of illustrative plates of the controlled valence state lithium titanate of lithium ion battery negative material prepared in above-described embodiment, coincide very well with the spinel lithium titanate standard diagram of stoichiometric proportion, still keeps spinel structure.
Fig. 3 is the XPS collection of illustrative plates of the controlled valence state lithium titanate of lithium ion battery negative material prepared in above-described embodiment, compared with the lithium titanate of the product stoichiometric proportion prepared with comparative example 1 provided by the invention, its Ti2p, in conjunction with being offset to 458.3eV from the 458.6eV of titanic Ti (IV), has produced titanous Ti (III).Through checking, owing to there is a certain amount of titanous, can make the controlled valence state lithium titanate of lithium ion battery negative material of the present invention there is higher conductivity compared to the lithium titanate of traditional stoichiometric proportion, its intrinsic conductivity is about 10
-6s/cm, than the proper conduction electricity rate 10 of the lithium titanate of stoichiometric proportion
-9s/cm wants a Senior Three order of magnitude.
The controlled valence state lithium titanate that Fig. 4 and Fig. 5 show lithium ion battery negative material of the present invention is made the relevant charging and discharging curve of half-cell.Wherein Fig. 4 is the charging and discharging curve of half-cell while not adding conductive agent, and its 0.2C and 1C reversible specific capacity are respectively 144mAh/g and 120mAh/g; And the lithium titanate of stoichiometric proportion prepared by comparative example 1 provided by the invention, reversible specific capacity is under the same conditions respectively 106mAh/g and 62mAh/g, show that controlled valence state lithium titanate of the present invention has good conductivity, also can discharge and recharge even if do not add conductive agent.Fig. 5 is the charging and discharging curve of half-cell while adding conductive agent, and its 0.2C and 1C embedding lithium platform are about respectively 1.539V (< 1.55V) and 1.504V; And the lithium titanate of stoichiometric proportion prepared by comparative example 1 provided by the invention, embedding lithium platform is under the same conditions about respectively 1.554V and 1.511V.Show to be offset to electronegative potential by the embedding lithium current potential of the controlled valence state lithium titanate of lithium ion battery negative material of the present invention, can make the voltage of the battery of preparation increase.
Fig. 6 shows the high power charging-discharging curve of the button half-cell that the controlled valence state lithium titanate of lithium ion battery negative material of the present invention makes, and the reversible specific capacity under 10C, 20C, 30C multiplying power is respectively 149mAh/g, 132mAh/g, 112mAh/g.And the lithium titanate of stoichiometric proportion prepared by comparative example 1 provided by the invention, respectively 141mAh/g, 115mAh/g of reversible specific capacity in the time of 10C, 20C, shows to have more excellent high rate charge-discharge by the embedding lithium electricity of the controlled valence state lithium titanate of lithium ion battery negative material of the present invention.
Embodiment 2
By lithium, titanium mol ratio Li: Ti=0.84: 1 takes He Tai source, lithium source.Lithium source in the present embodiment is lithium carbonate, gets 15.52 parts of lithium carbonates.Titanium source is rutile titanium dioxide, gets 39.94 parts of rutile titanium dioxides.The He Tai source, lithium source taking is mixed 2 hours in dry mixing device.He Tai source, mixed lithium source is placed in the high temperature furnace that is connected with air and rises to 900 DEG C with the programming rate of 10 DEG C/min, carry out sintering.After constant temperature 12 hours, cool to room temperature with the furnace.
Then to add in the material obtaining after sintering a certain amount of sucrose as additive and deionized water as solvent.Wherein, sucrose accounts for 0.5% of sintering resulting materials, and adding ionized water to make solid content is 20%, obtains the mixed liquor of proportioning.Above-mentioned mixed liquor is joined in Ultrafine Grinding, and ball milling is after 2 hours, and spraying is dry.
The material obtaining is risen to 700 DEG C with the programming rate of 5 DEG C/min in the high temperature furnace that is connected with high-purity argon gas, carry out double sintering, after constant temperature 6 hours, cool to room temperature with the furnace, resulting materials is lithium ion battery negative material of the present invention, concrete product is as shown in b container in Fig. 1, and it is blue that this lithium ion battery negative material is.
This lithium ion battery negative material product is made to button half-cell.While adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 165mAh/g and 140mAh/g, and embedding lithium platform is about respectively 1.539V and 1.504V; While not adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 140mAh/g and 118mAh/g, and embedding lithium platform is about respectively 1.534V and 1.501V.
Embodiment 3
By lithium, titanium mol ratio Li: Ti=0.82: 1 takes He Tai source, lithium source.Lithium source in the present embodiment is lithium hydroxide, gets 11.05 parts of lithium hydroxides.Titanium source is rutile titanium dioxide, gets 39.94 parts of rutile titanium dioxides.The He Tai source, lithium source taking is mixed 2 hours in dry mixing device.
He Tai source, mixed lithium source is placed in the high temperature furnace that is connected with air and rises to 750 DEG C with the programming rate of 5 DEG C/min, carry out sintering.After constant temperature 24 hours, cool to room temperature with the furnace.
Then to add in the material obtaining after sintering a certain amount of epoxy resin as additive and alcohol as solvent.Epoxy resin accounts for 10% of sintering resulting materials, and adding alcohol to make solid content is 33%, obtains the mixed liquor of proportioning.
Above-mentioned mixed liquor is joined and stirred in mill, and ball milling is after 4 hours, vacuum and heating drying.
The material obtaining is risen to 700 DEG C with the programming rate of 5 DEG C/min in the high temperature furnace that is connected with high-purity argon gas, carry out double sintering, constant temperature, after 12 hours, cools to room temperature with the furnace, resulting materials is lithium ion battery negative material of the present invention, and it is blue that this lithium ion battery negative material is.
This lithium ion battery negative material product is made to button half-cell.While adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 165mAh/g and 166mAh/g, and embedding lithium platform is about respectively 1.538V and 1.508V; While not adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 150mAh/g and 130mAh/g, and embedding lithium platform is about respectively 1.534V and 1.504V.
Embodiment 4
By lithium, titanium mol ratio Li: Ti=0.82: 1 takes He Tai source, lithium source.Lithium source in the present embodiment is lithium hydroxide, gets 11.05 parts of lithium hydroxides, and titanium source is rutile titanium dioxide, gets 39.94 parts of rutile titanium dioxides.The He Tai source, lithium source taking is mixed 2 hours in dry mixing device.He Tai source, mixed lithium source is placed in the high temperature furnace that is connected with air and rises to 800 DEG C with the programming rate of 5 DEG C/min, carry out sintering.After constant temperature 24 hours, cool to room temperature with the furnace.Then to add in the material obtaining after sintering a certain amount of polyvinyl resin as additive and acetone as solvent.Epoxy resin accounts for 3% of sintering resulting materials, and adding acetone to make solid content is 33%, obtains the mixed liquor of proportioning.Above-mentioned mixed liquor is joined and stirred in mill, and ball milling is after 4 hours, and heating evaporation is dry.
The material obtaining is risen to 600 DEG C with the programming rate of 5 DEG C/min in the high temperature furnace that is connected with high pure nitrogen, carry out double sintering, constant temperature, after 24 hours, cools to room temperature with the furnace, resulting materials is lithium ion battery negative material of the present invention, and it is blue that this lithium ion battery negative material is.
This lithium ion battery negative material product is made to button half-cell.While adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 165mAh/g and 160mAh/g, and embedding lithium platform is about respectively 1.539V and 1.507V; While not adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 155mAh/g and 140mAh/g, and embedding lithium platform is about respectively 1.533V and 1.503V.
Comparative example 1
By lithium, titanium mol ratio Li: Ti=0.80: 1 takes He Tai source, lithium source.Lithium source in the present embodiment is lithium carbonate, gets 15.15 parts of lithium carbonates.Titanium source is 39.94 parts of anatase titanium dioxides.The He Tai source, lithium source taking is mixed 2 hours in dry mixing device.He Tai source, mixed lithium source is placed in the high temperature furnace that is connected with air and rises to 750 DEG C with the programming rate of 10 DEG C/min, carry out sintering.After constant temperature 24 hours, cool to room temperature with the furnace.
Then in the material obtaining after sintering, add deionized water as solvent, and add ionized water to make solid content to be 33%, to obtain the mixed liquor of proportioning.Above-mentioned mixed liquor is joined in Ultrafine Grinding, and ball milling is after 10 hours, and spraying is dry.The material obtaining is risen to 600 DEG C with the programming rate of 5 DEG C/min in the high temperature furnace that is connected with high-purity argon gas, carry out double sintering, after constant temperature 6 hours, cool to room temperature with the furnace, obtain the lithium titanate of stoichiometric proportion, concrete product is as shown in c container in Fig. 1, and this lithium ion battery negative material is white in color, and its proper conduction electricity rate is about 10
-9s/cm.
This lithium ion battery negative material product is made to button half-cell.While adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 162mAh/g and 155mAh/g, and embedding lithium platform is about respectively 1.554V and 1.511V; And while not adding conductive agent, its 0.2C and 1C reversible specific capacity are respectively 106mAh/g and 62mAh/g, embedding lithium platform is about respectively 1.547V and 1.511V.Show for white lithium titanate, because conductivity is poor, if do not add conductive agent, its charge-discharge performance is greatly deteriorated.Reversible specific capacity 141mAh/g, 115mAh/g respectively in the time of 10C, the large multiplying power of 20C.
Claims (4)
1. a lithium ion battery negative material, is characterized in that, this lithium ion battery negative material is controlled valence state lithium titanate, and its chemical formula is: Li
4ti (IV)
5-xti (III)
xo
(12-x/2), wherein, 0 < x < 5; IV, III are respectively the valence state of Ti, and this lithium ion battery negative material structure is spinel structure, and the intrinsic conductivity of described lithium ion battery negative material is 10
-3～10
-8s/cm, embedding lithium current potential is lower than the lithium titanate Li of stoichiometric proportion
4ti
5o
12embedding lithium current potential, and embedding lithium current potential is 1.50～1.55V, reversible specific capacity is 120mAh/g～170mAh/g, can realize 1～20C rate charge-discharge, its appearance color of described lithium ion battery negative material is blue;
Described lithium ion battery negative material is prepared by a method comprising the following steps:
A, He Tai source, lithium source is mixed by lithium, titanium mol ratio Li:Ti=0.80～0.84:1;
B, the mixture in Yu Tai source, lithium source is warming up to 600～1000 DEG C with the programming rate of 1～50 DEG C/min in high temperature furnace, constant temperature 3～72 hours, cools to room temperature with the furnace, obtains the lithium titanate pure phase of stoichiometric proportion;
C, lithium titanate pure phase is first added to percentage by weight is the solvent that 0.5～10 additive and percentage by weight are 100%～900%, grind or Ultrafine Grinding carries out ball milling mixing by stirring, and be dried by heating evaporation seasoning, vacuum and heating drying method or spray drying process, described additive is one or more in glucose, sucrose, starch, polyvinyl alcohol, phenolic resins, epoxy resin and furfural resin, and described solvent is deionized water, ethanol or acetone;
D, will be dried after material put into high temperature furnace, under inert protective gas, be warming up to 600～900 DEG C with the programming rate of 1～50 DEG C/min, constant temperature 2～30 hours, after abundant reaction, is cooled to room temperature, obtains controlled valence state lithium titanate.
2. material as claimed in claim 1, the feature of preparing the method that this material adopts is also, and described lithium source is lithium carbonate, lithium hydroxide or lithium nitrate, and titanium source is the titanium dioxide of anatase, rutile, amorphous or brookite type.
3. material as claimed in claim 1, the feature of preparing the method that this material adopts is also, in step (b), the mixture in Yu Tai source, lithium source is warming up to 700～850 DEG C with the programming rate of 5～20 DEG C/min in high temperature furnace, constant temperature 12～48 hours, cool to room temperature with the furnace, obtain the lithium titanate pure phase of stoichiometric proportion; In step (d), after being dried, material is put into high temperature furnace, under inert protective gas, is warming up to 600～750 DEG C with the programming rate of 5～20 DEG C/min, and constant temperature 6～24 hours, after abundant reaction, is cooled to room temperature, obtains controlled valence state lithium titanate.
4. material as claimed in claim 1, the feature of preparing the method that this material adopts is also, in step (c), it is the solvent that 1～7.5 additive and percentage by weight are 200%～300% that lithium titanate pure phase is first added to percentage by weight, grind or Ultrafine Grinding carries out ball milling mixing by stirring, and by heating evaporation seasoning, vacuum and heating drying method or spray drying process are dried, described additive is glucose, sucrose, starch, polyvinyl alcohol, phenolic resins, one or more in epoxy resin and furfural resin, described solvent is deionized water, ethanol or acetone.
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