CN104229894A - Sol-gel method for preparation of lithium ion battery lithium molybdate cathode material - Google Patents
Sol-gel method for preparation of lithium ion battery lithium molybdate cathode material Download PDFInfo
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- CN104229894A CN104229894A CN201310237338.4A CN201310237338A CN104229894A CN 104229894 A CN104229894 A CN 104229894A CN 201310237338 A CN201310237338 A CN 201310237338A CN 104229894 A CN104229894 A CN 104229894A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a sol-gel method for preparation of a lithium ion battery lithium molybdate cathode material. The method includes the steps of: dissolving MoO3 powder in distilled water, stirring evenly in a magnetic stirrer, heating to 80 DEG C to form a grey white suspension solution, adding lithium salt to finally form a uniform and stable colloid, and conducting vacuum drying to obtain the lithium molybdate (Li2MoO4) cathode material. The method also comprises carbon coating of lithium molybdate (Li2MoO4) material, and synthesis of carbon coated lithium molybdate (Li2MoO4) is by adding a water soluble carbon coating material, lithium salt and molybdenum trioxide into distilled water, and conducting the above method. The material obtained by the above method has high actual capacity and excellent cycling performance. The invention is applicable to the production of high-performance lithium ion battery cathode material lithium molybdate (Li2MoO4).
Description
Technical field
The present invention relates to a kind of preparation method of ion secondary battery cathode material lithium, particularly a kind of sol-gel method synthesized high-performance lithium molybdate (Li
2moO
4) method of negative material.
Background technology
Lithium-ion secondary cell has many advantages: operating voltage is high, and the voltage of usual monomer lithium-ions battery is 3.6V, and the voltage of MH-Ni, Cd-Ni battery is 1.2V, differs 3 times; Volume is little, quality is light, specific energy high (specific energy is 3 times of lead acid cell, 2 times for all kinds of ni-type battery); Have extended cycle life, far above other battery; Charge safely and fast, self-discharge rate is low; Memory-less effect, duration of service is long.
Therefore, since Sony Corporation in 1991 releases commercial lithium-ions battery, the research about lithium-ions battery is in the ascendant.At present, mobile telephone, notebook computer and some other portable electric equipment use lithium-ions battery as power supply mostly.Further, its demand is increased more and more sooner.The foreseeable future, power truck (EV) or hybrid vehicle (HEV) are with the energy and be used for the large-scale energy-storage battery of storage of electrical energy and all may use lithium-ions battery, this makes the research about lithium-ions battery obtain huge power, thus enters the stage of accelerated development.
While greatly developing anode material for lithium-ion batteries, the exploration of people's anticathode material also never stops.Metallic lithium has the highest specific storage (3860mAh/ g) and the most negative electropotential (-3.045V is to standard hydrogen electrode), and therefore, as far back as the beginning of the seventies in last century, people just create great interest to lithium.But researchist find with metallic lithium be the lithium secondary battery of negative pole in process of charging, lithium an-ode easily forms dendrite, thus causes battery-heating, even explode.Within 1991, carbon negative pole material (poly furfuryl alcohol RESEARCH OF PYROCARBON) is successfully applied to commercial lithium-ion batteries by Sony, and the high-energy rechargeable cell that higher, the energy density of security almost can compare favourably with lithium secondary battery has in the world been born finally.Due to graphite, to possess electronic conductivity high afterwards thereupon, and lithium ion spread coefficient is large, and laminate structure volume change before and after embedding lithium is little, embedding lithium capacity high (300-350mAh/g) and low (the 0.1V vs Li/Li of intercalation potential
+) etc. advantage, become the commercial Li-ion battery negative material of current main flow.But due to the restriction of the structural performance of graphite own, the development of graphite cathode material also encounters bottleneck, such as specific storage, to reach capacity, can not meet the lasting large current discharging capability etc. required by large-sized power battery.Therefore people also turn one's attention to un-graphite materials, such as hard carbon and other non-carbon material.
First Desckanvers in 1971 etc. synthesize Li
1+xti
2-xo
4(0≤x≤1/3), and be studied.The people such as Kiyoshi and Ryosuke in 2002 report a kind of negative material Li with spinel structure
4ti
5o
12, it is 1.55V relative to the current potential of lithium electrode, and theoretical specific capacity is 175mAh/g, and actual specific capacity is 150 ~ 160mAh/g.At Li
+embedding with deviate from middle crystal formation and do not change, volume change is less than 1%, thus makes Li
4ti
5o
12there is the cycle performance more excellent than carbon.Meanwhile, the research of antimony, tin, silicon base compound and some metals and nonmetal oxide negative material also achieves very large achievement.
The present invention, by being applicable to the simple process of suitability for industrialized production, has synthesized a kind of lithium ion battery negative material-lithium molybdate (Li
2moO
4).At present also without any bibliographical information lithium molybdate (Li
2moO
4) application in lithium ion battery negative material.Content of the present invention shows, this material has higher theoretical specific capacity and actual specific capacity, lower discharge platform (0.5V).Therefore find and be suitable for suitability for industrialized production lithium molybdate (Li
2moO
4) the synthetic method beyond doubt significantly work of negative material.
Current lithium molybdate (Li
2moO
4) be generally all the method adopting high temperature process heat, this method is at synthesized high-performance lithium molybdate (Li
2moO
4) there is a lot of shortcoming in negative material aspect: first, it is even that raw material is difficult to dispersing and mixing, in order to make raw material be mixed fully, substantially all will take the method for secondary ball milling; Meanwhile, because raw material is difficult to the mixing that reaches on atomic level, in order to make it fully react in the process of reaction, generally all need the temperature of more than 500 DEG C and longer reaction times, and both inevitably brings increase and the reunion of product grain.Result of study according to us shows, the granule-morphology of product and the impact of size on lithium molybdate negative material performance are huge, has evenly and more short grained product has larger specific surface area, can bring the lifting on product property simultaneously.And higher temperature of reaction and long reaction times can reduce the chemical property of product undoubtedly.In addition, to be that the direct carbon of material is coated also bring difficulty for the method for high temperature process heat, and experiment shows, during higher than 500 DEG C, carbon material is to lithium molybdate (Li
2moO
4) there is carbothermic reduction effect.Therefore, a kind of new reaction method is adopted to be necessary to replace high temperature process heat method.
We have employed liquid phase (collosol and gel) synthesis method being more suitable for suitability for industrialized production, make reaction raw materials in liquid phase environment, reach Homogeneous phase mixing on atomic level, reduce temperature of reaction, avoid the generation of impurity phase; Meanwhile, under liquid phase state, add carbon encapsulated material, make covered effect evenly complete, thus greatly improve product property.
Summary of the invention
The object of the invention is to the shortcoming for existing high temperature process heat method, provide one to utilize sol-gel method synthesized high-performance lithium ion battery negative material lithium molybdate (Li
2moO
4) preparation method, carry out carbon to product coated, described method can Reaction time shorten, and reduce temperature of reaction, product has excellent chemical property simultaneously.With the lithium molybdate (Li of the method synthesis
2moO
4) negative material has higher charge/discharge capacity and preferably circulation and high rate performance.
A process for preparing sol-gel for lithium ion battery negative material lithium molybdate, it comprises the steps:
(1) molybdenum trioxide powder is dissolved in distilled water be placed in magnetic stirring apparatus to stir and is heated to 60 ~ 90 DEG C and forms canescence suspension liquids;
(2) added by lithium salts in the canescence suspension liquid that step (1) obtains, solution reacts, and forms colourless transparent solution, by solution stirring to dry, obtains the colloid of stable homogeneous;
(3) the colloid vacuum-drying in 80 ~ 90 DEG C will obtained, obtains white gels shape lithium molybdate (Li
2moO
4) negative material.
Further, in step (2), water-soluble carbon coating material and described lithium salts are together added in the canescence suspension liquid that step (1) obtains; The same process through step (3), puts into tube furnace by after the gel abrasive obtained, and under inert atmosphere or reducing atmosphere, 250 ~ 450 DEG C of isothermal holding 4 ~ 6 hours, obtain the lithium molybdate (Li that carbon is coated after naturally cooling
2moO
4) negative material.
In above-mentioned preparation method, in described lithium salts and molybdic oxide colloid, the mol ratio of lithium, molybdenum is 2:1.
In above-mentioned preparation method, described in step (2), lithium salts is Quilonum Retard (Li
2cO
3), Lithium Acetate (CH
3cOOLi), lithium oxalate (Li
2c
2o
4), lithium hydroxide (LiOH), lithium nitrate (LiNO
3) in one.
In above-mentioned preparation method, described water-soluble carbon coating material be by carbon, hydrogen, oxygen three kinds elementary composition, water-soluble, carbon compound can be produced at high temperature lower than cracking under the anaerobic state of temperature of reaction.
In above-mentioned preparation method, described water-soluble carbon coating material is the one in sucrose, glucose, citric acid, Mierocrystalline cellulose and starch; The add-on of water-soluble carbon coating material meets amount that its cracking produces carbon and accounts for and finally obtain the coated lithium molybdate (Li of carbon
2moO
4) negative material weight total amount 1 ~ 20%.
In above-mentioned preparation method, described inert atmosphere is nitrogen (N
2), argon gas (Ar), carbonic acid gas (CO
2) or helium (He) in one.
In above-mentioned preparation method, described reducing atmosphere is Ar/H
2gas mixture, N
2/ H
2one in gas mixture, hydrogen, ammonia or carbon monoxide (CO).
The present invention compared with prior art, has the following advantages:
(1) adopt the method for collosol and gel of liquid phase to carry out mixing raw material, make reaction raw materials in liquid phase environment, reach Homogeneous phase mixing on atomic level, thus avoid the generation of impurity phase.
(2) reduce temperature of reaction, Reaction time shorten, product grain is even, and specific surface area is large, and performance is higher, has the cycle performance that higher reversible capacity is become reconciled.Meanwhile, reduce production cost, make reaction process be convenient to control.
(3) under liquid phase state, add carbon encapsulated material, make covered effect evenly complete, thus improve product property.
The substantive distinguishing features that the present invention gives prominence to and marked improvement can be embodied from following examples, but they do not do any restriction to the present invention.
Accompanying drawing explanation
In Fig. 1, curve (a) and (b) are the X ray diffracting spectrum of embodiment 1, embodiment 2 respectively;
Fig. 2 be embodiment 1 first charge-discharge (curve a and b) and second time discharge curve (curve c), wherein: charge-discharge magnification is 0.2C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Fig. 3 be embodiment 1 first charge-discharge (curve a and b) and second time discharge curve (curve c), wherein, charge-discharge magnification is respectively 0.5C, and charging/discharging voltage scope is 0.1 ~ 2.5V;
Fig. 4 is the cycle performance curve of embodiment 1, and wherein: charge-discharge magnification is 0.2C and 0.5C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Fig. 5 a and Fig. 5 b is the stereoscan photograph of the different amplification of embodiment 2 product respectively;
Fig. 6 be embodiment 2 first charge-discharge (curve a and b) and second time discharge curve (curve c), wherein: charge-discharge magnification is 0.2C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Fig. 7 be embodiment 2 first charge-discharge (curve a and b) and second time discharge curve (curve c), wherein: charge-discharge magnification is 0.5C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Fig. 8 is the cycle performance curve of embodiment 2, and wherein: charge-discharge magnification is 0.2C and 0.5C, charging/discharging voltage scope is 0.1 ~ 2.5V;
In Fig. 9, curve a and curve b is the X ray diffracting spectrum of embodiment 3, embodiment 4 respectively;
Figure 10 be embodiment 3 first charge-discharge (curve a and b) and second time discharge curve (curve c), wherein: charge-discharge magnification is 0. 3C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Figure 11 is the cycle performance curve of embodiment 3, and wherein: charge-discharge magnification is 0.3C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Figure 12 be embodiment 4 first charge-discharge (curve a and b) and second time discharge curve (curve c), wherein: charge-discharge magnification is 0.15C, charging/discharging voltage scope is 0.1 ~ 2.5V;
Figure 13 is the cycle performance curve of embodiment 4, and wherein: charge-discharge magnification is 0. 13C, charging/discharging voltage scope is 0.1 ~ 2.5V.
Figure 14 is the cycle performance curve of embodiment 4 under multiple different multiplying, wherein: charging/discharging voltage scope is 0.1 ~ 2.5V.
Embodiment
Below in conjunction with example and accompanying drawing, specific embodiment of the invention is described further, but enforcement of the present invention and protection are not limited thereto.
embodiment 1
3.6168g molybdenum trioxide powder is dissolved in distilled water to be placed in magnetic stirring apparatus to stir and is heated to 80 DEG C and to form canescence suspension liquids; Added in the canescence suspension liquid of formation by 1.8850g Quilonum Retard (Li:Mo=2:1 mol ratio), solution reacts, and forms colourless transparent solution after 10 minutes, obtains white colloidal after 5 hours; By the colloid 80 DEG C of vacuum-dryings obtained, after 24 hours, obtain white gels shape lithium molybdate negative material.The X-ray diffractogram of product is shown in a curve in Fig. 1, and as seen from the figure, the lithium molybdate negative material of tripartite's crystal formation of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high.This lithium molybdate negative material is in 0.1 ~ 2.5V voltage range, and as shown in Figure 2 and Figure 3, cycle performance as shown in Figure 4 for first charge-discharge when multiplying power is respectively 0.2C and 0.5C and second time discharge curve.Can find out, under 0.2C multiplying power, first charge-discharge capacity is 300.8mAh/g and 711.8mAh/g, second time loading capacity is 327.3mAh/g, under 0.5C multiplying power, first charge-discharge capacity is 392.2mAh/g and 918.3mAh/g, second time loading capacity is 373.1mAh/g, and discharge platform is at about 0.4V.No matter be charging and discharging curve or cyclic curve, after can seeing electric discharge first, negative material has the loss of comparatively large capacity, and we by its formation owing to SEI film in discharge process first, can hinder Li in following working cycle (discharge process)
+embedding, the irreversible loss of the capacity that causes.However, without the lithium molybdate negative material that carbon is coated shown under low range can with current commercialization graphite (300-350mAh/g, Li
+/ Li<0.1V) comparable actual capacity and safer sparking voltage.
embodiment 2
3.6168g molybdenum trioxide powder is dissolved in distilled water to be placed in magnetic stirring apparatus to stir and is heated to 80 DEG C and to form canescence suspension liquids; By 1.8850g Quilonum Retard (Li:Mo=2:1 mol ratio), the relative molybdic oxide of 16wt%(and Quilonum Retard total amount) citric acid (0.88g) add in the canescence suspension liquid of formation, solution reacts, form colourless transparent solution after 10 minutes, after 5 hours, obtain white colloidal; By the colloid 80 DEG C of vacuum-dryings obtained, white gels shape product is obtained after 24 hours, products therefrom grinding is placed in tube furnace and is heated to 400 DEG C, isothermal holding 6 hours under high-purity argon (Ar) atmosphere, after naturally cooling, obtain the coated lithium molybdate negative material of carbon.The X-ray diffractogram of product is shown in b curve in Fig. 1, and as seen from the figure, the coated lithium molybdate negative material of tripartite's crystal formation carbon of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high, and covered effect is good.The scanning electron microscopic picture of this product is shown in Fig. 5, can see that product presents length and is about 5 μm of tubular morphology, and the carbon granule of nanoscale is dispersed in the gap of tube and tube, clearly this kind of coated rear presented tubular morphology of carbon significantly can improve specific surface area and the specific conductivity of material, electrolytic solution and negative active core-shell material is fully contacted thus product is had to circulate and high rate performance preferably.The coated lithium molybdate negative material of this carbon is in 0.1 ~ 2.5V voltage range, and as shown in Figure 6, Figure 7, cycle performance as shown in Figure 8 for first charge-discharge when multiplying power is respectively 0.2C and 0.5C and second time discharge curve.Can find out, under 0.2C multiplying power, first charge-discharge capacity is 608.9mAh/g and 961.3mAh/g, second time loading capacity is 607.3mAh/g, under 0.5C multiplying power, first charge-discharge capacity is 631mAh/g and 1015.3mAh/g, second time loading capacity is 631.6mAh/g, and discharge platform is at about 0.4V.For the lithium molybdate negative material of the non-bag carbon of embodiment 1, can see that the material after bag carbon to be all greatly improved improvement at charge/discharge capacity or cycle performance under identical multiplying power, make lithium molybdate negative material more have competitive power in lithium ion battery negative material.
embodiment 3
1.4467g molybdenum trioxide powder is dissolved in distilled water to be placed in magnetic stirring apparatus to stir and is heated to 80 DEG C and to form canescence suspension liquids; By 2.0608g lithium acetate (Li:Mo=2:1 mol ratio), the relative molybdic oxide of 10wt%(and Quilonum Retard presoma total amount) glucose (0.3033g) add the canescence suspension liquid of formation, solution reacts, form colourless transparent solution after 10 minutes, after 5 hours, obtain blackish green colloid; By the colloid 80 DEG C of vacuum-dryings obtained, after 24 hours, obtain brown gel-like product, products therefrom grinding is placed in tube furnace and is heated to 300 DEG C, at nitrogen (N
2) isothermal holding 4 hours under atmosphere, obtain the coated lithium molybdate negative material of carbon after naturally cooling.The X-ray diffractogram of product is shown in a curve in Fig. 9, and as seen from the figure, the coated lithium molybdate negative material of tripartite's crystal formation carbon of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high, and covered effect is good.The coated lithium molybdate negative material of this carbon in 0.1 ~ 2.5V voltage range, multiplying power be 0. 3C first charge-discharge and second time discharge curve as shown in Figure 10, cycle performance is as shown in figure 11.Can find out, under 0.3C multiplying power, first charge-discharge capacity is 631.7mAh/g and 1082.5mAh/g, and second time loading capacity is 640.3mAh/g, shows good cycle characteristics simultaneously.
embodiment 4
2.4112g molybdenum trioxide powder is dissolved in distilled water to be placed in magnetic stirring apparatus to stir and is heated to 80 DEG C and to form canescence suspension liquids; By 1.5541g lithium hydroxide Li:Mo=2:1 mol ratio), the relative molybdic oxide of 12wt%(and Quilonum Retard total amount) sucrose (0.4802g) add in the canescence suspension liquid of formation, solution reacts, form colourless transparent solution after 10 minutes, after 5 hours, obtain white colloidal; By the colloid 80 DEG C of vacuum-dryings obtained, after 24 hours, obtain white gels shape product, products therefrom grinding is placed in tube furnace and is heated to 300 DEG C, at Ar/H
2isothermal holding 4 hours under gas mixture atmosphere, obtains the coated lithium molybdate negative material of carbon after naturally cooling.The X-ray diffractogram of product is shown in b curve in Fig. 9, and as seen from the figure, the coated lithium molybdate negative material of tripartite's crystal formation carbon of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high, and covered effect is good.The coated lithium molybdate negative material of this carbon in 0.1 ~ 2.5V voltage range, multiplying power be 0.15C first charge-discharge and second time discharge curve as shown in figure 12, cycle performance is as shown in figure 13.Can find out, under 0.15C multiplying power, first charge-discharge capacity is 692.3mAh/g and 1085.6mAh/g, and second time loading capacity is 712.1mAh/g, and after 23 circulations, discharge capacitance is 84.3%, shows good cycle characteristics.Figure 14 is the cycle performance curve of embodiment 4 under multiple different multiplying, wherein: charging/discharging voltage scope is 0.1 ~ 2.5V.Can find out up under the charge-discharge magnification of 10C, the coated lithium molybdate negative material of carbon still has the specific storage of 100mAh/g, and after the test of 24C, the negative material getting back to 0.33C still has the reversible capacity of 350mAh/g, describe carbon coated after lithium molybdate as lithium ion battery negative material, there is excellent performance.
As can be seen from the above-described embodiment, to lithium molybdate negative material carry out carbon coated after, material electrochemical performance has had and has significantly improved.As can be seen from X ray diffracting spectrum, carbon material add the crystalline phase not changing lithium molybdate, effectively can reduce the reunion of crystal grain because the Erbium-doped of carbon mixes on the contrary, make production die less, specific surface area increases, thus improves the ion diffusion rates of product; Carbon is to the coated electronic conductivity that improve product of lithium molybdate simultaneously, and therefore, the lithium molybdate negative material after coated has higher specific discharge capacity than not coated.
Claims (8)
1. a process for preparing sol-gel for lithium ion battery lithium molybdate negative material, is characterized in that comprising the steps:
(1) molybdenum trioxide powder is dissolved in distilled water be placed in magnetic stirring apparatus to stir and is heated to 60 ~ 90 DEG C and forms canescence suspension liquids;
(2) added by lithium salts in the canescence suspension liquid that step (1) obtains, solution reacts, and forms colourless transparent solution, by solution stirring to dry, obtains the colloid of stable homogeneous;
(3) the colloid vacuum-drying in 60 ~ 90 DEG C will obtained, obtains white gels shape lithium molybdate (Li
2moO
4) negative material.
2. the process for preparing sol-gel of a kind of lithium ion battery lithium molybdate negative material according to claim 1, it is characterized in that in step (2), water-soluble carbon coating material and described lithium salts are together added in the canescence suspension liquid that step (1) obtains; The same process through step (3), puts into tube furnace by after the gel abrasive obtained, and under inert atmosphere or reducing atmosphere, 250 ~ 450 DEG C of process 4 ~ 6 hours, obtain the lithium molybdate (Li that carbon is coated after naturally cooling
2moO
4) negative material.
3. preparation method according to claim 1 and 2, is characterized in that the mol ratio of lithium, molybdenum in described lithium salts and molybdic oxide colloid is 2:1.
4. preparation method according to claim 1 and 2, is characterized in that described in step (2), lithium salts is Quilonum Retard (Li
2cO
3), Lithium Acetate (CH
3cOOLi), lithium oxalate (Li
2c
2o
4), lithium hydroxide (LiOH), lithium nitrate (LiNO
3) in one.
5. preparation method according to claim 2, it is characterized in that described water-soluble carbon coating material be by carbon, hydrogen, oxygen three kinds elementary composition, water-soluble, carbon compound can be produced at high temperature lower than cracking under the anaerobic state of temperature of reaction.
6. preparation method according to claim 2, is characterized in that described water-soluble carbon coating material is the one in sucrose, glucose, citric acid, Mierocrystalline cellulose and starch; The add-on of water-soluble carbon coating material meets amount that its cracking produces carbon and accounts for the coated lithium molybdate (Li of the carbon that finally obtains
2moO
4) negative material weight total amount 1 ~ 20%.
7. preparation method according to claim 2, is characterized in that described inert atmosphere is nitrogen (N
2), argon gas (Ar), carbonic acid gas (CO
2) or helium (He) in one.
8. preparation method according to claim 2, is characterized in that described reducing atmosphere is Ar/H
2gas mixture, N
2/ H
2one in gas mixture, hydrogen, ammonia or carbon monoxide (CO).
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| CN114349051A (en) * | 2021-12-31 | 2022-04-15 | 欣旺达电动汽车电池有限公司 | Multi-metal molybdate, preparation method thereof and lithium ion battery |
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