CN102163716A - Modified spinel lithium manganate material and preparation method thereof as well as battery positive material comprising material - Google Patents
Modified spinel lithium manganate material and preparation method thereof as well as battery positive material comprising material Download PDFInfo
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- CN102163716A CN102163716A CN2011100636460A CN201110063646A CN102163716A CN 102163716 A CN102163716 A CN 102163716A CN 2011100636460 A CN2011100636460 A CN 2011100636460A CN 201110063646 A CN201110063646 A CN 201110063646A CN 102163716 A CN102163716 A CN 102163716A
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Abstract
The invention discloses a modified spinel lithium manganate material and a preparation method thereof as well as a battery positive material comprising the material. A vanadium element is doped in the modified spinel lithium manganate material, and the molar ratio of Li to Mn to V is (0.96-1.12):(1.80-2):(0.001-0.05). The modified spinel lithium manganate material provided by the invention has the advantages of stable structure, regular topography, excellent processing property and good electrochemistry property; and in the preparation method of the modified spinel lithium manganate material, the used high temperature solid synthesis method has the characteristics of low cost, simple process flow and wide parameter control range, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of spinelle manganic acid lithium material and preparation method thereof, in particular to trace doped modified spinelle manganic acid lithium material of a kind of V element and preparation method thereof, and the positive electrode for battery material of making by modified spinelle manganic acid lithium material.
Background technology
In recent years, anode material for lithium-ion batteries is from single cobalt acid lithium material, the stage of developing into the polynary application of multiple material such as cobalt acid lithium, LiMn2O4, lithium nickelate, ternary material, LiFePO4.Cobalt acid lithium, ternary material need rare, the expensive metallic cobalt of ample resources when synthetic, thereby cost of raw material height; The poor heat stability of the cobalt of Charging state acid lithium, lithium nickelate makes with it to be that the battery of positive electrode is not good enough in the fail safe under the abuse conditions; The voltage platform of ternary material, LiFePO4 is low, makes it can't satisfy more and more higher operating voltage requirement.And spinel lithium manganate has that resource is extensive, cheap, charge and discharge platform is high, advantages such as fail safe is good under the abuse condition, progressively becomes the particularly positive electrode of the first-selection of power lithium-ion battery of lithium ion battery of future generation.But shortcomings such as spinel lithium manganate ubiquity volumetric specific energy is low, high temperature cyclic performance difference improve volumetric specific energy and improve the scientific research development direction that high temperature cyclic performance is a spinel lithium manganate.
At present, usually improve the volumetric specific energy of spinel lithium manganate by the method that improves density of material, improve density of material improving its volumetric specific energy as Chinese invention patent CN200410096259.7, CN200410009004.2, CN200610140909.2, CN200910019098.4 etc. by the method for preparing spherical lithium manganate, but all there is the shortcoming of complex technical process, cost height, large-scale production poor stability in these methods.Chinese invention patent CN200910193819.3 improves density of material to improve its volumetric specific energy by multi-element doping and high temperature solid phase synthesis by the multistep sintering.Chinese invention patent CN200910019320.0 then adopts the high temperature solid phase synthesis that adds organic facies to prepare the LiMn2O4 second particle to improve material to improve its volumetric specific energy, there is following shortcoming in above-mentioned technology: 1) raw material reaction is even inadequately, reaction time is long, causes pattern irregularity, the thing of LiMn2O4 mutually inhomogeneous; 2) synthesis temperature height, the easy structure that a spot of dephasign occurs and easily form anoxic in the product, the chemical property of deterioration material; 3) synthetic warm area multistage or repeatedly synthetic, the reaction time is long, and the energy consumption height is unfavorable for the reduction of synthetic cost.
Summary of the invention
The present invention aims to provide a kind of modified spinelle manganic acid lithium material and preparation method thereof, with the low and technical problems such as modified spinelle manganic acid lithium material complex manufacturing, cost height and large-scale production poor stability of volumetric specific energy that solve spinelle manganic acid lithium material in the prior art.
According to an aspect of the present invention, provide a kind of modified spinelle manganic acid lithium material, be doped with v element in the modified spinelle manganic acid lithium material, wherein, the mol ratio of Li: Mn: V is 0.96～1.12: 1.80～2: 0.001～0.05.
Further, the mol ratio of Li: Mn: V is 1.02～1.10: 1.90～2.00: 0.001～0.01.
Further, modified spinelle manganic acid lithium material is made of the primary particle secondary agglomeration particle form of reuniting, primary particle be shaped as the nearly octahedral bodily form and its average grain diameter greater than 1 μ m.
Further, the diameter of primary particle is 1.5～30 μ m, and the specific area of modified spinelle manganic acid lithium material is 0.2～0.8m
2/ g.
According to another aspect of the present invention, a kind of preparation method of above-mentioned modified spinelle manganic acid lithium material is provided, may further comprise the steps: with lithium carbonate, electrolytic manganese dioxide with to contain the vanadium alloy be 0.96～1.12: 1.80～2 according to the mol ratio of Li: Mn: V: 0.001～0.05 mixed is even, obtains the lithium carbonate mixture; The lithium carbonate mixture is carried out the high temperature solid-state synthetic reaction under 650 ℃～950 ℃, obtain modified spinelle manganic acid lithium material; Wherein, the high temperature solid-state synthetic reaction is the once sintered technology of single warm area.
Further, contain the vanadium alloy and be selected from vanadium trioxide, vanadic oxide, vanadium trichloride, the ammonium metavanadate one or more.
Further, the lithium carbonate mixture carries out the high temperature solid-state synthetic reaction under 750 ℃～850 ℃, and the constant temperature time of this high temperature solid-state synthetic reaction is 8～20 hours.
According to a further aspect of the invention, provide a kind of positive electrode for battery material, this positive electrode is formed through the crushing and classification Processing of Preparation by above-mentioned modified spinelle manganic acid lithium material.
Modified spinelle manganic acid lithium material provided by the invention, trace doped, reduced production cost, and product compacted density height, energy density per unit volume improves, and Stability Analysis of Structures, pattern is regular, processing characteristics is excellent, high conformity; The method of this modified spinelle manganic acid lithium material of production provided by the invention, flow process is simple, and the parameter control range is wide in range, the large-scale production good stability.The positive electrode for battery material list of being made by modified spinelle manganic acid lithium material reveals good electrochemical trend.
Description of drawings
Figure of description is used to provide further understanding of the present invention, constitutes a part of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, does not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 shows the SEM figure of the modified spinelle manganic acid lithium of embodiment 1 preparation;
Fig. 2 shows the XRD figure of the modified spinelle manganic acid lithium of embodiment 1 preparation;
Fig. 3 shows the SEM figure of the spinel lithium manganate of Comparative Examples preparation; And
Fig. 4 shows the XRD figure of the spinel lithium manganate of Comparative Examples preparation.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the feature among the embodiment among the present invention can make up mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
According to an aspect of the present invention, provide a kind of modified spinelle manganic acid lithium material, be doped with v element in this modified spinelle manganic acid lithium material, wherein, the mol ratio of Li: Mn: V is 0.96～1.12: 1.80～2: 0.001～0.05.Modified spinelle manganic acid lithium material of the present invention, by introducing trace doped element V, help on the one hand synthetic mutually evenly, Stability Analysis of Structures, pattern is regular, processing characteristics is excellent, high conformity, on the other hand, metal doping has reduced production cost because of need not to cost an arm and a leg in a large number.In other execution modes of the present invention, modified spinelle manganic acid lithium material is not limited only to Li, Mn and three kinds of elements of V, can also add other elements according to actual needs.Preferably, the mol ratio of Li in the modified spinelle manganic acid lithium material: Mn: V is 1.02～1.10: 1.90～2.00: 0.001～0.01.
Modified spinelle manganic acid lithium material of the present invention is made of the secondary agglomeration particle that the primary particle reunion that is shaped as the nearly octahedral bodily form forms, and the average grain diameter of primary particle is greater than 1 μ m, be preferably 1.5～30 μ m, the specific area of this material is simultaneously: 0.2～0.8m
2/ g.
According to another aspect of the present invention, a kind of preparation method of modified spinelle manganic acid lithium material is provided, may further comprise the steps: with lithium carbonate, electrolytic manganese dioxide with to contain the vanadium alloy be 0.96～1.12: 1.80～2 according to the mol ratio of Li: Mn: V: 0.001～0.05 mixed is even, obtains the lithium carbonate mixture; The lithium carbonate mixture is carried out the high temperature solid-state synthetic reaction under 650 ℃～950 ℃, obtain modified spinelle manganic acid lithium material; Wherein, the high temperature solid-state synthetic reaction is the once sintered technology of single warm area, and the once sintered technology of the single warm area of indication promptly refers under a fixed temperature above-mentioned lithium carbonate mixture sintering certain hour, keeps temperature-resistant in the whole sintering process.The constant temperature time of high temperature solid-state synthetic reaction kept 6～50 hours.
The present invention adopts the once sintered synthesis technique of this single warm area to prepare spinel lithium manganese oxide anode material, needing in the high temperature solid phase synthesis in the prior art to have avoided energy waste synthetic by multistep and that a plurality of warm area sintering cause, therefore with low cost, flow process is simple, the parameter control range is wide in range, good stability in batches, is fit to large-scale production.
The present invention is not particularly limited the compound of lithium, the compound of manganese, is preferably lithium carbonate and electrolytic manganese dioxide.The lithium content of lithium carbonate is high and little to the corrosivity of equipment, and electrolytic manganese dioxide is low than the compound cost of other manganese, simultaneously, owing to both wide material sources, makes and is easier to, and obtains easily from market.Further, element V is derived from least a in vanadium trioxide, vanadic oxide, vanadium trichloride, the ammonium metavanadate.Preferably, element V is derived from vanadic oxide, and vanadic oxide itself has electro-chemical activity and obtains easily.Be that other vanadium-containing compounds are as long as can satisfy purity requirement all in invention which is intended to be protected with being appreciated that.Preferably, the reaction temperature of lithium carbonate mixture is 750 ℃～850 ℃.Temperature is low excessively, and the crystallization of synthetic product is not sufficiently complete, and temperature is too high, and synthetic product easily forms the structure of anoxic.Preferably, the reaction time of lithium carbonate mixture is 8～20 hours.Use the spinel lithium manganese oxide anode material of technical scheme preparation provided by the invention and manufacture battery, the positive plate compacted density is at 2.8g/cm
3More than, the gram volume that discharges first can reach more than the 108mAh/g, and has excellent cycle performance.The spinel lithium manganese oxide anode material of technical scheme preparation provided by the invention is fit to mix use with other positive electrodes such as cobalt acid lithium, ternary material, LiFePO4s, also is fit to independent active material as lithium ion cell positive and uses.
Embodiment 1
Adopt following steps to prepare the modified spinelle manganic acid lithium positive electrode:
(1) selecting purity for use is that 99.5% lithium carbonate (LITHIUM BATTERY), purity are that 92% electrolytic manganese dioxide (EMD) is a raw material, analyze pure vanadic oxide as the V source, according to Li: Mn: V=1.08: 1.92: 0.008 mol ratio is carried out weighing and burden, mode by dry ball milling mixes.
(2) with the above-mentioned material that mixes, place in the pushed bat kiln 800 ℃ of constant temperature 10 hours, cooling then.
(3) the resulting powder of step (2) is carried out the simple crushing classification and promptly obtain the modified spinelle manganic acid lithium positive electrode.
Adopt following steps to prepare the modified spinelle manganic acid lithium positive electrode:
(1) selecting purity for use is that 99.5% lithium carbonate (LITHIUM BATTERY), purity are that 92% electrolytic manganese dioxide (EMD) is a raw material, analyze pure vanadic oxide as the V source, according to Li: Mn: V=0.96: 1.95: 0.05 mol ratio is carried out weighing and burden, mode by dry ball milling mixes.
(2) the above-mentioned material that mixes is placed in the pushed bat kiln,, cool off according to designing requirement then 650 ℃ of constant temperature 40 hours.
(3) the resulting powder of step (2) is carried out the simple crushing classification and promptly obtain the modified spinelle manganic acid lithium positive electrode.
Embodiment 3
Adopt following steps to prepare the modified spinelle manganic acid lithium positive electrode:
(1) selecting purity for use is that 99.5% lithium carbonate (LITHIUM BATTERY), purity are that 92% electrolytic manganese dioxide (EMD) is a raw material, analyze pure vanadic oxide as the V source, according to Li: Mn: V=1.12: 1.88: 0.001 mol ratio is carried out weighing and burden, mode by dry ball milling mixes.
(2) the above-mentioned material that mixes is placed in the pushed bat kiln, 950 ℃ of constant temperature 8 hours cools off according to designing requirement then.
(3) the resulting powder of step (2) is carried out the simple crushing classification and promptly obtain the modified spinelle manganic acid lithium positive electrode.
Comparative Examples
Adopt following steps to prepare spinel lithium manganese oxide anode material:
(1) selecting purity for use is that 99.5% lithium carbonate (LITHIUM BATTERY), purity are that 92% electrolytic manganese dioxide (EMD) is a raw material, and according to Li: Mn=1.08: 1.92 mol ratio is carried out weighing and burden, by the mode of dry ball milling, mixes.
(2) the above-mentioned material that mixes is required and the production capacity designing requirement according to art designs, place in the pushed bat kiln, 800 ℃ of constant temperature 10 hours cools off according to designing requirement then.
(3) the resulting powder of step (2) is carried out the simple crushing classification and promptly obtain spinel lithium manganese oxide anode material.
The XRD performance test: XRD performance test (anodal material sample is carried out x-ray diffraction pattern (CuKa) experiment) is carried out on RINT2000 vertical goniometer type x-ray diffractometer.Experiment condition is: radiation source CuK α
Operating voltage 40kV, operating current 250mA adopts continuous sweep, and sweep limits 2 θ are 10 °～85 °, and going on foot wide is 0.02 °, and sweep speed is 2 °/min.
The SEM performance test: the JSM-6360LV scanning electron microscopy that adopts Japanese JEOL company to produce is carried out microstructural observation to synthetic sample, and grain size and size are analyzed, the primary particle diameter as shown in Table 1.
BET performance test: on the QuadraSorb Station 1 type specific surface tester that adopts U.S. Kang Ta company to produce anodal material sample is carried out the BET performance test.
The gram volume that discharges first test: make flexible packing lithium ion battery with the Delanium material as negative material and test, measuring current density is 2mA/cm
2, voltage range records the gram volume of discharge first of material between 3.0V～4.2V.
Table one
As shown in Table 1, the spinel lithium manganese oxide anode material of Application Example 1, embodiment 2 and embodiment 3 preparations is made battery, and the compacted density of pole piece is respectively 2.95g/cm
3, 2.81g/cm
3, 2.80g/cm
3And the spinel lithium manganese oxide anode material of the Comparative Examples of the vanadium that do not mix preparation, the compacted density of pole piece only is 2.53g/cm
3, illustrate and adopt the compacted density of the prepared modified spinelle manganic acid lithium positive electrode of technical scheme of the present invention to be greatly improved that energy density per unit volume improves.Make flexible packing lithium ion battery with the Delanium material as negative material and test, measuring current density is 2mA/cm
2Voltage range is between 3.0V～4.2V, the gram volume of discharge first that records the modified spinelle manganic acid lithium positive electrode of embodiment 1, embodiment 2 and embodiment 3 preparations is respectively 110.9mAh/g, 108.3mAh/g, 108.1mAh/g, promptly adopt the gram volume of discharge first that technical scheme of the present invention prepares the modified spinelle manganic acid lithium positive electrode all more than 108mAh/g, and embodiment 1 have higher pole piece compacted density; The numbers illustrated of BET specific area in the consolidated statement one, it is little to adopt technical scheme of the present invention to prepare the spinel lithium manganese oxide anode material specific area, and promptly the crystal grain volume is big, has good processing properties.
Compare with XRD figure (Fig. 3,4) with the SEM of the spinel lithium manganate of Comparative Examples preparation, from the SEM of the modified spinelle manganic acid lithium of embodiment 1 preparation and XRD figure (Fig. 1,2) as can be seen, adopt regular, the high conformity of spinel lithium manganate pattern of technical solution of the present invention preparation, illustrate that it has good processing properties.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a modified spinelle manganic acid lithium material is characterized in that, is doped with v element in the described modified spinelle manganic acid lithium material, and wherein, the mol ratio of Li: Mn: V is 0.96～1.12: 1.80～2: 0.001～0.05.
2. modified spinelle manganic acid lithium material according to claim 1 is characterized in that, the mol ratio of described Li: Mn: V is 1.02～1.10: 1.90～2.00: 0.001～0.01.
3. modified spinelle manganic acid lithium material according to claim 1 and 2, it is characterized in that, described modified spinelle manganic acid lithium material is made of the primary particle secondary agglomeration particle form of reuniting, described primary particle be shaped as the nearly octahedral bodily form and its average grain diameter greater than 1 μ m.
4. modified spinelle manganic acid lithium material according to claim 3 is characterized in that, the diameter of described primary particle is 1.5～30 μ m, and the specific area of described modified spinelle manganic acid lithium material is 0.2～0.8m
2/ g.
5. the preparation method of each described modified spinelle manganic acid lithium material in the claim 1 to 4 is characterized in that, may further comprise the steps:
With lithium carbonate, electrolytic manganese dioxide with to contain the vanadium alloy be 0.96～1.12: 1.80～2 according to the mol ratio of Li: Mn: V: 0.001～0.05 mixed is even, obtains the lithium carbonate mixture;
Described lithium carbonate mixture is carried out the high temperature solid-state synthetic reaction under 650 ℃～950 ℃, obtain described modified spinelle manganic acid lithium material;
Wherein, described high temperature solid-state synthetic reaction is the once sintered technology of single warm area.
6. preparation method according to claim 5 is characterized in that, the described vanadium alloy that contains is selected from vanadium trioxide, vanadic oxide, vanadium trichloride, the ammonium metavanadate one or more.
7. preparation method according to claim 5 is characterized in that, described lithium carbonate mixture carries out the high temperature solid-state synthetic reaction under 750 ℃～850 ℃, and described high temperature solid-state synthetic reaction constant temperature time is 8～20 hours.
8. a positive electrode for battery material is characterized in that, is formed through the crushing and classification Processing of Preparation by each described modified spinelle manganic acid lithium material among the claim 1-4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394290A (en) * | 2011-11-18 | 2012-03-28 | 青岛华冠恒远锂电科技有限公司 | Anode material of lithium ion battery and preparation method thereof |
| CN106532033A (en) * | 2015-09-09 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method for mixed lithium manganate material |
| CN109830655A (en) * | 2019-01-07 | 2019-05-31 | 新乡市中天新能源科技股份有限公司 | A kind of ion co-doped method for preparing lithium manganate having spinel structure positive electrode |
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2011
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| JPH07272765A (en) * | 1994-03-31 | 1995-10-20 | Sony Corp | Nonaqueous electrolytic secondary battery and its manufacture |
| CN1490250A (en) * | 2002-10-18 | 2004-04-21 | 北京圣比和科技有限公司 | Preparing method for spinel potassium manganate as lithium ion battery anode of electric vehicle |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394290A (en) * | 2011-11-18 | 2012-03-28 | 青岛华冠恒远锂电科技有限公司 | Anode material of lithium ion battery and preparation method thereof |
| CN106532033A (en) * | 2015-09-09 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method for mixed lithium manganate material |
| CN109830655A (en) * | 2019-01-07 | 2019-05-31 | 新乡市中天新能源科技股份有限公司 | A kind of ion co-doped method for preparing lithium manganate having spinel structure positive electrode |
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Application publication date: 20110824 |