CN102195033A - Method for preparing lithium battery anode material Li-Mn compound oxide at low temperature and lithium ion secondary battery - Google Patents
Method for preparing lithium battery anode material Li-Mn compound oxide at low temperature and lithium ion secondary battery Download PDFInfo
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Abstract
The invention relates to a method for preparing lithium battery anode material Li-Mn compound oxide at a low temperature and a lithium ion secondary battery. The Li-Mn compound oxide is spinel-shaped Li-Mn compound oxide LiMn(2-y)XyO4 doped with other metal elements X, wherein, X is at least one of cobalt, nickel, copper, zinc, chromium, and aluminum, and Y is more than 0 and less than or equal to 0.1. The method comprises the following steps: stirring the compound of manganese and X and 8-55% of excessive lithium compound in deionized water in a stoichiometric ratio of a final product LiMn(2-y)XyO4; carrying out ultrasonic treatment; stirring again, and carrying out hydro-thermal reaction at the temperature of 160-280 DEG C; washing, filtering, centrifuging and separating the product; drying and carrying out heat treating on the product at the temperature of 300-550 DEG C to obtain the Li-Mn compound oxide. The invention also discloses a lithium ion secondary battery taking the material as the anode material. The Li-Mn compound oxide provided by the invention has uniform particles, stable structure, good crystallinity, simple technique process and low cost; and the prepared lithium battery has excellent charge-discharge circulation performance.
Description
Technical field
The present invention relates to a kind of low temperature and prepare the method for anode material of lithium battery complex Li-Mn-oxide and the lithium rechargeable battery for preparing with this positive electrode, belong to the preparing technical field of anode material for lithium-ion batteries and lithium rechargeable battery.
Background technology
Development of science and technology, human life quality's raising; Petroleum resources face a crisis, ball ecological environment goes from bad to worse, and have formed the science and technology in novel secondary cell and associated materials field and the dual social background of industry fast development.On the one hand, be making rapid progress of Information technology and information industry, mobile phone, notebook computer, panoramic portable electronics emerge in an endless stream; On the other hand, air pollution, the not enough century-old caution of earth petroleum reserves make that human demand at different purposes searching new green powers is extremely urgent.At present, the exploitation and the industrialization of mobile model high-tech device are highly relying on specific energy height, removable, resource-conserving, can use repeatedly, green energy resource storage device free from environmental pollution.The active demand in market is arisen at the historic moment novel secondary cell.Wherein, lithium ion battery is as state-of-the art secondary cell, owing to its superior performance enjoys favor.For lithium ion battery, positive electrode still all occupies important status at aspect of performance at cost.Advantages such as the LiMn2O4 of spinel structure has aboundresources, cost is low, fail safe good, overcharging resisting, pollution are little, easy recycling, its industrial applications for reduce the lithium ion battery cost, to widen application very useful.This shows, research and develop spinel lithium manganese oxide anode material cheap, excellent performance and will have vast market prospect and huge economic benefit, and the dependence that reduces Chinese cobalt resource import is had very important strategic importance.
At present, researchers are carrying out extensive work aspect the preparation of lithium cell anode material lithium manganate, as, high temperature solid phase synthesis (1. Liu D, Liu X, He Z (2007) J Alloys Compd 436:387-391; 2. Ha H-W, Yun N J, Kim K (2007) Electrochim Acta 52:3236-3241.), sol-gel processing (1. C.J.Curtis, J.X.Wang, D.L.Schulz, J.Electrochem.Soc.151 (2004) A590; 2. Arumugam D, Kalaignan GP (2008) J ElectroanalChem624:197-204.), hard template method (J.Cabana, T.Valdes-Solis, M.R.Palacin, J.Oro-Sole, A.Fuertes, G.Marban, A.B.Fuertes, J.Power Sources 166 (2007) 492.) etc.These preparation methods all in various degree the electrical property that makes manganate cathode material for lithium improve; but; all there is certain shortcoming in said method: as; though solid phase method is the main method of present scale; has the control that is easy to simple to operate; technological process is short; realize advantages such as suitability for industrialized production easily, still, its weak point is that energy consumption is big; efficient is low; prescription control difficulty, the uniformity of target material is relatively poor, and grinding needs fully; calcination time is of a specified duration, and the target product chemical property of preparation is relatively poor relatively.And above-mentioned other liquid phase rule exists technological operation relative complex, cost higher, does not only fit into industrial large-scale production, and still can not satisfy the secondary lithium battery shortcomings such as requirement more and more higher to manganate cathode material for lithium in the practical application.
Summary of the invention
One of purpose of the present invention is in order to overcome the weak point on the above-mentioned prior art, provides that simple, the required prices of raw and semifnished materials of a kind of method of operation are cheap, production cost is low, is beneficial to the lithium battery complex Li-Mn-oxide positive electrode of environmental protection.
Two of purpose of the present invention provides that a kind of crystallinity is good, the lithium battery complex Li-Mn-oxide positive electrode of Stability Analysis of Structures, the preparation of employing low temperature method.
Three of purpose of the present invention provides a kind of charge/discharge capacity and charge-discharge performance is good, long service life, electric performance stablity, make the lithium ion battery of positive electrode with the complex Li-Mn-oxide of the present invention's preparation.
The present invention realizes above-mentioned purpose in the following manner, and described complex Li-Mn-oxide is the spinel type lithium manganese complex oxide LiMn that is doped with other metallic element X
2-yX
yO
4, wherein, X is at least a in cobalt, nickel, copper, zinc, chromium, the aluminium, the X element of preferred doping way for mixing more than 2 kinds or 2 kinds, 0＜y≤0.1.
A kind of low temperature prepares the method for anode material of lithium battery spinel structure lithium-manganese composite oxides, and this method is carried out successively as follows:
(1) with the compound of manganese and X element with end product LiMn
2-yX
yO
4Stoichiometric proportion and the lithium compound of excessive 8～55wt% in appropriate amount of deionized water, fully stir 0.5～3h;
(2) mixture with step (1) gained is that 28～200kHz, power are wide-ultra sonicated 0.5～3h of 100～300W in frequency, and magnetic agitation 0.5～2h changes it over to reactor at last and makes the packing volume of reactor reach 75% then;
(3) with the mixture hydro-thermal reaction 18～40h in 160～280 ℃ temperature range in step (2) reactor, reaction makes reactor reduce to room temperature naturally after finishing;
(4) with the product in the step (3) through deionized water and absolute ethyl alcohol fully wash, filtration or centrifugation, at 70～120 ℃ of vacuumize 4～12h, promptly get the spinel structure lithium-manganese composite oxides then;
(5) in order to obtain the spinel structure lithium-manganese composite oxides that crystallinity is good, structure is more stable, can be with dried product in the step (4) at 300～550 ℃ of heat treatment 1～10h.
Among the above-mentioned preparation method, described manganese source compound is manganese dioxide, manganese nitrate, manganese sulfate, manganese carbonate, potassium permanganate or manganese chloride; Used lithium compound comprises the hydroxide of lithium salts or lithium, and described lithium salts comprises at least a in lithium chloride, lithium iodide, lithium bromide, lithium sulfate, lithium hydrogen sulfate, lithium carbonate, lithium bicarbonate, lithium nitrate, the lithium oxalate; The source compound of described X element comprises hydroxide, oxide or the salt of X element.
With the above-mentioned spinel structure lithium-manganese composite oxides of the present invention preparation positive active material as lithium rechargeable battery, the positive pole that uses this positive active material to constitute prepares lithium rechargeable battery, and carries out performance test.Particular content comprises: the positive pole of battery is by the complex Li-Mn-oxide LiMn of 85%～95wt%
2-yX
y0
4Prepare as solvent as binding agent, an amount of N-methyl pyrrolidone as the acetylene black of positive electrode active materials, 2wt%～10wt% polyvinylidene fluoride (PVDF) as conductive agent, 2wt%～10wt%, above-mentioned material is prepared into slurry with certain viscosity and flowability after stirring, adopt the collector of aluminium foil then as positive plate, slurry evenly is coated on the aluminium foil, strikes out anodal disk after drying.The negative pole of battery is the lithium sheet, and electrolyte is for containing 1mol/LLiF
6EC: the organic electrolyte of DEC (mass ratio is 1: 1), barrier film is a polypropylene microporous film.To adopt the button cell of method for preparing to test with lithium-ion battery tester, the charging deboost during test be 4.30V, and final discharging voltage is 3.00V, and charging and discharging currents density is 0.5mA/cm
3Under this test condition, the first charge-discharge specific capacity of prepared sample is all greater than 110mAh/g; First charge-discharge efficiency is greater than 90%; The 100th charge and discharge cycles rear platform capacity ratio be still greater than 85%, and promptly the lithium ion battery of doing the positive active material preparation by the prepared complex Li-Mn-oxide of the present invention has good electrical property.
Owing to adopted above-mentioned preparation method and step, good effect of the present invention is:
(1) the present invention adopts Hydrothermal Preparation spinel structure lithium ion battery anode material of lithium manganese composite oxide, and this method provides that a kind of method of operation is simple, production cost is low, has been beneficial to the method for preparing the lithium battery anode material lithium manganese composite oxide of environmental protection.
(2) method for preparing the lithium battery anode material lithium manganese composite oxide provided by the present invention, can under the cryogenic conditions in 280～280 ℃ of temperature ranges, obtain spinel structure lithium ion battery anode material of lithium manganese composite oxide, also hydrothermal product can be heat-treated 1～10h in 300～550 ℃ temperature range, to obtain the lithium battery anode material lithium manganese composite oxide that crystallinity is better, structure is more stable.Compare with solid-phase synthesis, the required hydrothermal temperature of this preparation technology, perhaps the heat treatment temperature after the hydro-thermal is all lower, can cut down the consumption of energy greatly.
(3) the present invention adopts the mode of one or more metal ion mixings in preparation process, strengthened the structural stability of complex Li-Mn-oxide anode material for lithium-ion batteries in the charge and discharge cycles process, the positive pole that constitutes with this positive active material prepares lithium rechargeable battery, can effectively suppress the John-Teller effect, alleviate the distortion of lattice that the dissolving owing to manganese causes, thereby obtain that charge-discharge performance is good, the lithium ion battery of structure and electric performance stablity.
Embodiment
Embodiment 1
The preparation chemical general formula is LiMn
1.98Cr
0.02O
4Lithium ion battery complex Li-Mn-oxide positive electrode.Take by weighing the lithium hydroxide of a certain amount of manganese dioxide, manganese chloride, chromic nitrate and excessive 8wt% by stoichiometric proportion, with its abundant magnetic agitation 0.5h in deionized water, in frequency is that 28kHz, power are ultrasonic Treatment 0.5h under the condition of 100W, and then magnetic agitation 0.5h, at last it is changed over to reactor and make the packing volume of reactor reach 75%, at 280 ℃ of hydro-thermal reaction 16h, reaction makes reactor reduce to room temperature naturally after finishing.With product through deionized water and absolute ethyl alcohol fully wash, filtration or centrifugation, at 70 ℃ of vacuumize 12h, promptly get the spinel structure lithium-manganese composite oxides then.In order to obtain the spinel structure lithium-manganese composite oxides that crystallinity is good, structure is more stable, can be with above-mentioned dried product at 300 ℃ of heat treatment 10h.
To have carried out heat treated manganese composite oxide after above-mentioned convection drying or the drying again as active substance of lithium ion battery anode, add acetylene black, PVDF and an amount of N-methyl pyrrolidone, according to the method described in the summary of the invention it is assembled into button cell and carries out electric performance test.Wherein, the quality percentage composition of manganese composite oxide, acetylene black and PVDF is respectively 85wt%, 5wt% and 10wt%.When the charging deboost be 4.30V, final discharging voltage is 3.00V, charging and discharging currents density is 0.5mA/cm
3The time, the first charge-discharge specific capacity of battery is 116mAh/g, first charge-discharge efficiency is that 95%, the 50 charge and discharge cycles rear platform capacity ratio is 89%.
Embodiment 2
The preparation chemical general formula is LiMn
1.9Cu
0.08Al
0.02O
4Lithium ion battery complex Li-Mn-oxide positive electrode.Take by weighing the lithium carbonate of a certain amount of manganese dioxide, manganese nitrate, chromic nitrate, copper nitrate and excessive 55wt% by stoichiometric proportion, with its abundant magnetic agitation 3h in deionized water, in frequency is that 200kHz, power are ultrasonic Treatment 2h under the condition of 300W, and then magnetic agitation 2h, at last it is changed over to reactor and make the packing volume of reactor reach 75%, at 160 ℃ of hydro-thermal reaction 40h, reaction makes reactor reduce to room temperature naturally after finishing.With product through deionized water and absolute ethyl alcohol fully wash, filtration or centrifugation, at 120 ℃ of vacuumize 4h, promptly get the spinel structure lithium-manganese composite oxides then.In order to obtain the spinel structure lithium-manganese composite oxides that crystallinity is good, structure is more stable, can be with above-mentioned dried product at 550 ℃ of heat treatment 1h.
To have carried out heat treated manganese composite oxide after above-mentioned convection drying or the drying again, according to the method described in the embodiment 1 it is assembled into button cell and carries out electric performance test as active substance of lithium ion battery anode.Wherein, the quality percentage composition of manganese composite oxide, acetylene black and PVDF is respectively 95wt%, 2wt% and 3wt%.When the charging deboost be 4.30V, final discharging voltage is 3.00V, charging and discharging currents density is 0.5mA/cm
3The time, the first charge-discharge specific capacity of battery is 122mAh/g, first charge-discharge efficiency is that 96%, the 50 charge and discharge cycles rear platform capacity ratio is 88%.
Embodiment 3
The preparation chemical general formula is LiMn
1.92Cr
0.02Cu
0.08Ni
0.02Zn
0.01Al
0.02O
4Lithium ion battery complex Li-Mn-oxide positive electrode.Take by weighing the lithium nitrate of a certain amount of manganese dioxide, manganese sulfate, chromic nitrate, copper nitrate, nickel nitrate, zinc nitrate, aluminum nitrate and excessive 15wt% by stoichiometric proportion, with its abundant magnetic agitation 1h in deionized water, in frequency is that 32kHz, power are ultrasonic Treatment 1.5h under the condition of 200W, and then magnetic agitation 1.5h, at last it is changed over to reactor and make the packing volume of reactor reach 75%, at 240 ℃ of hydro-thermal reaction 24h, reaction makes reactor reduce to room temperature naturally after finishing.With product through deionized water and absolute ethyl alcohol fully wash, filtration or centrifugation, at 90 ℃ of vacuumize 8h, promptly get the spinel structure lithium-manganese composite oxides then.In order to obtain the spinel structure lithium-manganese composite oxides that crystallinity is good, structure is more stable, can be with above-mentioned dried product at 400 ℃ of heat treatment 4h.
To have carried out heat treated manganese composite oxide after above-mentioned convection drying or the drying again, according to the method described in the embodiment 1 it is assembled into button cell and carries out electric performance test as active substance of lithium ion battery anode.Wherein, the quality percentage composition of manganese composite oxide, acetylene black and PVDF is respectively 85wt%, 10wt% and 5wt%.When the charging deboost be 4.30V, final discharging voltage is 3.00V, charging and discharging currents density is 0.5mA/cm
3The time, the first charge-discharge specific capacity of battery is 119mAh/g, first charge-discharge efficiency is that 93%, the 50 charge and discharge cycles rear platform capacity ratio is 86%.
Embodiment 4
The preparation chemical general formula is LiMn
1.97Cu
0.02Cr
0.01O
4Lithium ion battery complex Li-Mn-oxide positive electrode.Take by weighing the lithium hydroxide of a certain amount of manganese dioxide, potassium permanganate, chromic nitrate, copper nitrate and excessive 30wt% by stoichiometric proportion, with its abundant magnetic agitation 2h in deionized water, in frequency is that 36kHz, power are ultrasonic Treatment 1.5h under the condition of 240W, and then magnetic agitation 1h, at last it is changed over to reactor and make the packing volume of reactor reach 75%, at 240 ℃ of hydro-thermal reaction 36h, reaction makes reactor reduce to room temperature naturally after finishing.With product through deionized water and absolute ethyl alcohol fully wash, filtration or centrifugation, at 100 ℃ of vacuumize 6h, promptly get the spinel structure lithium-manganese composite oxides then.In order to obtain the spinel structure lithium-manganese composite oxides that crystallinity is good, structure is more stable, can be with above-mentioned dried product at 450 ℃ of heat treatment 6h.
To have carried out heat treated manganese composite oxide after above-mentioned convection drying or the drying again, according to the method described in the embodiment 1 it is assembled into button cell and carries out electric performance test as active substance of lithium ion battery anode.Wherein, the quality percentage composition of manganese composite oxide, acetylene black and PVDF is respectively 90wt%, 8wt% and and 2wt%.When the charging deboost be 4.30V, final discharging voltage is 3.00V, charging and discharging currents density is 0.5mA/cm
3The time, the first charge-discharge specific capacity of battery is 120mAh/g, first charge-discharge efficiency is that 93%, the 50 charge and discharge cycles rear platform capacity ratio is 87%.
Claims (7)
1. a low temperature prepares the method and the lithium rechargeable battery of anode material of lithium battery complex Li-Mn-oxide, it is characterized in that, with the compound of manganese and X element with end product LiMn
2-yX
yO
4Stoichiometric proportion and the lithium compound of excessive 8～55wt% in deionized water for stirring, ultrasonic Treatment, stir once more, in 160～280 ℃ temperature range, carry out hydro-thermal reaction then, product through washing, dry or with dried product heat treatment after promptly get complex Li-Mn-oxide with spinel structure.
2. preparation method according to claim 1 is characterized in that, described complex Li-Mn-oxide is the spinel structure lithium-manganese composite oxides LiMn that is doped with other metallic element X
2-yX
yO
4, wherein, X is at least a in cobalt, nickel, copper, zinc, chromium, the aluminium, 0＜y≤0.1.
3. preparation method according to claim 1 is characterized in that, a kind of X element in the claim 2 of mixing at least in the described complex Li-Mn-oxide, and preferred doping way is the X element in the claim 1 more than 2 kinds or 2 kinds that mixes.
4. preparation method according to claim 1 is characterized in that, preparation complex Li-Mn-oxide LiMn
2-yX
yO
4The time, used manganese source compound is manganese dioxide, manganese nitrate, manganese sulfate, manganese carbonate, potassium permanganate or manganese chloride; Used lithium compound comprises the hydroxide of lithium salts or lithium, and described lithium salts comprises at least a in lithium chloride, lithium iodide, lithium bromide, lithium sulfate, lithium hydrogen sulfate, lithium carbonate, lithium bicarbonate, lithium nitrate, the lithium oxalate; The source compound of described X element comprises hydroxide, oxide or the salt of X element.
5. preparation method according to claim 1 is characterized in that, the method that the low temperature preparation has the complex Li-Mn-oxide of spinel structure may further comprise the steps:
(1) with the compound of manganese and X element with end product LiMn
2-yX
yO
4Stoichiometric proportion and the lithium compound of excessive 8～55wt% in appropriate amount of deionized water, fully stir 0.5～3h;
(2) mixture with step (1) gained is that 28～200kHz, power are wide-ultra sonicated 0.5～3h of 100～300W in frequency, and magnetic agitation 0.5～2h changes it over to reactor at last and makes the packing volume of reactor reach 75% then;
(3) with the mixture hydro-thermal reaction 18～40h in 160～280 ℃ temperature range in step (2) reactor, reaction makes reactor reduce to room temperature naturally after finishing;
(4) with the product in the step (3) through deionized water and absolute ethyl alcohol fully wash, filtration or centrifugation, at 70～120 ℃ of vacuumize 4～12h, promptly get the spinel structure lithium-manganese composite oxides then;
(5) in order to obtain the spinel structure lithium-manganese composite oxides that crystallinity is good, structure is more stable, can be with dried product in the step (4) at 300～550 ℃ of heat treatment 1～10h.
6. lithium ion secondary battery anode is characterized in that using the complex Li-Mn-oxide of middle step (4) of claim (5) or step (5) preparation as positive active material.
7. lithium rechargeable battery is characterized in that using the positive pole of the complex Li-Mn-oxide of middle step (4) of claim (5) or step (5) preparation as the positive active material formation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872307A (en) * | 2014-03-26 | 2014-06-18 | 哈尔滨工业大学 | Method for preparing aluminum-oxide-cladding nano lithium manganate composite material by electrostatic self-assembling method |
| CN105244475A (en) * | 2015-11-14 | 2016-01-13 | 福建师范大学 | Composite spinel material, preparing method thereof and application thereof |
| CN107346815A (en) * | 2016-05-06 | 2017-11-14 | 成都中科来方能源科技股份有限公司 | Secondary battery of zinc-lithium-manganese water system and preparation method thereof |
| CN107507969A (en) * | 2017-08-11 | 2017-12-22 | 芜湖天弋能源科技有限公司 | A kind of modified spinelle manganic acid lithium material, preparation method and applications |
| CN115974161A (en) * | 2022-03-28 | 2023-04-18 | 贵州大龙汇成新材料有限公司 | Manganous manganic oxide pre-intercalated lithium intermediate and preparation method and application thereof |
| CN116053471A (en) * | 2023-03-08 | 2023-05-02 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
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| CN101038965A (en) * | 2006-03-14 | 2007-09-19 | 深圳市比克电池有限公司 | Method for preparing modified spinelle manganic acid lithium material and lithium secondary battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103872307A (en) * | 2014-03-26 | 2014-06-18 | 哈尔滨工业大学 | Method for preparing aluminum-oxide-cladding nano lithium manganate composite material by electrostatic self-assembling method |
| CN105244475A (en) * | 2015-11-14 | 2016-01-13 | 福建师范大学 | Composite spinel material, preparing method thereof and application thereof |
| CN107346815A (en) * | 2016-05-06 | 2017-11-14 | 成都中科来方能源科技股份有限公司 | Secondary battery of zinc-lithium-manganese water system and preparation method thereof |
| CN107507969A (en) * | 2017-08-11 | 2017-12-22 | 芜湖天弋能源科技有限公司 | A kind of modified spinelle manganic acid lithium material, preparation method and applications |
| CN115974161A (en) * | 2022-03-28 | 2023-04-18 | 贵州大龙汇成新材料有限公司 | Manganous manganic oxide pre-intercalated lithium intermediate and preparation method and application thereof |
| CN116053471A (en) * | 2023-03-08 | 2023-05-02 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
| CN116053471B (en) * | 2023-03-08 | 2023-08-18 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
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| CN102195033B (en) | 2014-06-04 |
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