CN102931389A - Lithium ion battery cathode material ZnMnO3 porous microsphere and application - Google Patents

Lithium ion battery cathode material ZnMnO3 porous microsphere and application Download PDF

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Publication number
CN102931389A
CN102931389A CN2012104441292A CN201210444129A CN102931389A CN 102931389 A CN102931389 A CN 102931389A CN 2012104441292 A CN2012104441292 A CN 2012104441292A CN 201210444129 A CN201210444129 A CN 201210444129A CN 102931389 A CN102931389 A CN 102931389A
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ion battery
lithium ion
porous microsphere
znmno
negative material
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沈强
赵陈浩
康文裴
王欣欣
赵世强
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Shandong University
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Shandong University
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    • 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

Abstract

The invention discloses a lithium ion battery cathode material ZnMnO3 porous microsphere and application thereof. Soluble manganese salt and zinc salt serve as raw materials of the ZnMnO3 porous microsphere, sodium carbonate serves as precipitator, is subjected to precipitation at the room temperature and then is filtered, sediment are collected, and finally calcination is conducted to obtain the porous microsphere. The ZnMnO3 porous microsphere serves as a lithium ion battery cathode material, under the rate of 500mAg-1, the primary discharge capacity and the second discharge capacity are respectively 1289.8 mAhg-1 and 813.6 mAhg-1, after 100 times of constant current charging-discharging circulation, the capacity is maintained at the level of about 736.9 mAhg-1, good electrochemical performance is showed, a guiding function is achieved for the development of novel lithium ion battery materials, the method is easy to operate and the porous microsphere can be produced and popularized on a large scale.

Description

A kind of lithium ion battery negative material ZnMnO 3Porous microsphere and application
Technical field
The invention belongs to technical field of electrochemistry, relate to a kind of material and application thereof of new type lithium ion battery negative pole, relate in particular to a kind of lithium ion battery negative material ZnMnO by the coprecipitation preparation 3Porous microsphere and the application in the preparation lithium ion battery with high energy density thereof.
Background technology
The lithium ion battery that exploitation has higher energy density, better cyclical stability and fail safe is the focus of new energy technology research always, considers relatively low (the theoretical capacity 372mAh g of specific capacity of the graphite as anode material for lithium-ion battery that generally uses now -1), have the more transition metal oxide of height ratio capacity (500-1000mAh g -1) more and more cause numerous scholars' concern (Energy Environ.Sci., 2011,4,2682.).
Embed from the conventional graphite negative pole and to deviate from the Mechanism of Electrochemistry of storage different, transition metal oxide is mainly realized the storage of energy by the redox reaction process.France Tarascon group (Nature 2000,407,496.) at first is studied in detail this class material, finds that its operating voltage is high and cyclical stability is relatively poor.So reduce its charge and discharge platform voltage and improve its cyclical stability and become one of focus of this research.Hispanic Tirado seminar is doing a lot of work aspect this class Novel anode material exploring, their reported first binary composite metal oxide (Chem.Mater.2002,14,2847); Discovery is compared with single oxide, and composite oxides have unique electrochemical behavior.Along with going deep into of research, the scientific worker further finds the transiton metal binary oxides ZnM of zinc-base 2O 4(M=Co, Fe, Cr and V) showed the cyclical stability that higher charge/discharge capacity is become reconciled.Wherein, ZnMn 2O 4Because nontoxic, raw material is easy to get especially, and charged electrical forces down the favor (J.Mater.Chem.2012,22,827) that advantages such as (than the low approximately 0.5V of iron) is subject to people.As a kind of transiton metal binary oxides that has equally the Zn-Mn-O component, the ZnMnO of Emission in Cubic 3Obtained widely research as magnetic material, it is the ZnMnO of 25nm that the method by oxalate co-precipitation such as Seehra has prepared average-size 3Nano particle, and studied the relation (Appl.Phys.Lett.2012,100,252407) of magnetic and structure.Magrez etc. have also prepared bar-shaped ZnMnO by the method that nitric acid decomposes 3Nano particle, the while has also been studied the magnetic performance (Solid StateCommun.2011,151,487) of product.But Emission in Cubic ZnMnO 3As research and the application of lithium ion battery negative material, even do not report; Simultaneously, according to ZnMn 2O 4Good chemical property, novel Zn MnO 3The worth expectations such as micro-nano preparation, chemical property and development and use thereof as lithium ion battery negative material.
The preparation method of binary metal oxide is more, mainly comprises solid phase method, chemical coprecipitation, hydro-thermal or solvent-thermal method, micro emulsion method and template.Utilizing chemical coprecipitation is by the raw material soluble-salt is dissolved in the solvent uniformly, under the effect of precipitation reagent, can form the co-precipitation with molecular level dispersion.And then heat-treat, obtain the target transiton metal binary oxides.Compare coprecipitation to have a cost relatively low with additive method, the advantages such as reaction condition gentleness.Based on ZnCO 3And MnCO 3Has similar solubility (ZnCO 3: K Sp=1.46 * 10 -10, MnCO 3: K Sp=2.34 * 10 -11), use the method for carbonic acid co-precipitation to prepare the carbonic acid zinc-manganese co-precipitation of binary, and then carry out high-temperature process and obtain target product ZnMnO 3, compare at aspects such as large-scale productions with other method and to have significant advantage.
Summary of the invention
For Novel cathode material for lithium ion battery ZnMnO 3Development Status, the problem to be solved in the present invention provides a kind of lithium ion battery negative material ZnMnO 3Porous microsphere and application.
Technical scheme of the present invention is to have designed a kind of easy chemical coprecipitation, and take soluble manganese salt and zinc salt as raw material, sodium carbonate is precipitation reagent.At room temperature slaine and sodium carbonate are dissolved in respectively in the water, then under agitation in metal salt solution, add sodium carbonate liquor, ageing number minute.Filtration obtains presoma carbonic acid zinc-manganese, then calcines at a certain temperature a few hours to obtain ZnMnO 3Porous microsphere.Use at last the ZnMnO that makes 3Porous microsphere and acetylene black and binding agent (sodium alginate) are mixed and made into electrode slice; Electrode slice is formed button cell in glove box, at room temperature measure its charge/discharge capacity and cycle performance, with check ZnMnO 3Porous microsphere is as the chemical property of lithium ion battery negative material.
Concrete, lithium ion battery negative material ZnMnO of the present invention 3Porous microsphere makes by the following method:
(1) with soluble manganese salt and soluble zinc salt in molar ratio for 1:1 joins in the deionized water, stir, be made into the colourless solution that total amount of substance is 5～20mmol/10mL;
(2) mol ratio in sodium carbonate and the described soluble manganese salt of step (1) and zinc salt is the ratio of 1.0:1～2.0:1, adds sodium carbonate liquor in the described solution of step (1), stirs 20～40min, obtains white suspension;
(3) with step (2) gained white suspension suction filtration, water, ethanol are respectively washed 3～5 times again, obtain white powder, then white powder are dried in 80 ± 10 ℃ baking oven;
(4) colourless powder of drying was calcined 2～8 hours under 400～800 ℃, the black powder that obtains is ZnMnO 3Porous microsphere.
Wherein: the described soluble manganese salt of step (1) and soluble zinc salt are manganese acetate and zinc acetate or manganese nitrate and zinc nitrate.
Above-mentioned lithium ion battery negative material ZnMnO 3In the porous microsphere: total amount of substance of the described soluble manganese salt of step (1) and soluble zinc salt is preferably 8～12mmol/10mL.
Above-mentioned lithium ion battery negative material ZnMnO 3In the porous microsphere: the mol ratio of the described sodium carbonate of step (2) and the described soluble manganese salt of step (1) and zinc salt is preferably 1.05:1～1.2:1.
Above-mentioned lithium ion battery negative material ZnMnO 3In the porous microsphere: the described calcining heat of step (5) is preferably 500～700 ℃, and calcination time is preferably 3～6 hours.
Lithium ion battery negative material ZnMnO of the present invention 3The application of porous microsphere in the preparation lithium ion battery with high energy density.
Wherein, the method for optimizing of described application is: by weight taking by weighing ZnMnO for the ratio of 8:1:25 3Porous microsphere, acetylene black and 2wt% sodium alginate soln are prepared into electrode slice and are assembled into button cell with the method for routine.
The present invention utilizes simple chemical coprecipitation to prepare the comparatively desirable ZnMnO of chemical property 3Porous microsphere (seeing Fig. 1, Fig. 2), and studied first its chemical property as lithium ion battery negative material.Namely at room temperature measure button cell charge/discharge capacity and the cycle performance made from test method, check ZnMnO 3Porous microsphere is as the chemical property of lithium ion battery negative material.
Result of the test shows: at 500mA g -1Speed under, for the first time and for the second time discharge capacity is respectively 1289.8 and 813.6mAh g -1, after 100 constant current charge-discharge circulations, its capacity also remains on 736.9mAh g -1Left and right sides (see figure 3) has represented good cycle performance, indicates lithium ion battery negative material ZnMnO of the present invention 3Porous microsphere has potential application in the lithium ion battery field.
Preparation ZnMnO of the present invention 3The method of porous microsphere is easy to operation, is easy to large-scale production, the porous ZnMnO that is synthesized 3Microballoon can enlarge the kind of lithium ion battery negative material, overcomes the low shortcoming of conventional carbon negative material specific capacity, and the exploitation Novel cathode material for lithium ion battery is had directive function.
Description of drawings
The ZnMnO that Fig. 1 is prepared 3The XRD figure of porous microsphere.
Fig. 2 ZnMnO 3The SEM picture of porous microsphere low power (a) and high power (b).
Fig. 3 ZnMnO 3The chemical property figure of porous microsphere.
Embodiment
Embodiment 1:
The porous ZnMnO that is used for lithium ion battery negative material 3Microballoon can make by the following method:
(1) is manganese acetate and zinc acetate (mol ratio 1:1) the adding deionized water of 20mmol with total amount of substance, stirs and form colourless solution (10mL);
(2) dropwise add the sodium carbonate liquor of 60mL, 0.4mol/L in the solution of step (1), stir about 30 minutes generates the suspension of white;
(3) the direct suction filtration of suspension that step (2) is obtained, water, ethanol are respectively washed three times again, obtain white powder, dry in 80 ℃ of baking ovens;
(4) white powder that step (3) is obtained is calcined 4h in 600 ℃ of high temperature resistance furnaces, obtain ZnMnO 3Porous microsphere.
Embodiment 2:
(1) is manganese acetate and zinc acetate (mol ratio 1:1) the adding 10mL deionized water of 10mmol with total amount of substance, stirs and form colourless solution;
(2) dropwise add the sodium carbonate liquor of 60mL, 0.3mol/L in the solution of step (1), stir about 30min generates the suspension of white
(3) the direct suction filtration of suspension that step (2) is obtained, water, ethanol are respectively washed three times again, obtain white powder, dry in 80 ℃ of baking ovens;
(4) white powder that step (3) is obtained is calcined 4h in 600 ℃ of high temperature resistance furnaces, obtain ZnMnO 3Porous microsphere.
Embodiment 3:
The porous ZnMnO that is used for lithium ion battery negative material 3Microballoon can make by the following method:
(1) is manganese nitrate and zinc nitrate (mol ratio 1:1) the adding 10mL deionized water of 10mmol with total amount of substance, stirs and form colourless solution;
(2) dropwise add the sodium carbonate liquor of 60mL, 0.2mol/L in the solution of step (1), stir about 30min generates the suspension of white;
(3) the direct suction filtration of suspension that step (2) is obtained, water, ethanol are respectively washed three times again, obtain white powder, dry in 80 ℃ of baking ovens;
(4) white powder that step (3) is obtained is calcined 4h in 700 ℃ of high temperature resistance furnaces, obtain ZnMnO 3Porous microsphere.
Embodiment 4:
(1) with soluble manganese salt and soluble zinc salt in molar ratio for 1:1 joins in the deionized water, stir, be made into the colourless solution that total amount of substance is 10mmol/10mL;
(2) mol ratio in sodium carbonate and the described soluble manganese salt of step (1) and zinc salt is the ratio of 1.1:1, adds sodium carbonate liquor in the described solution of step (1), stirs 30min, obtains white suspension;
(3) with step (2) gained white suspension suction filtration, water, ethanol are respectively washed 3 times again, obtain white powder, then white powder are dried in 80 ± 1 ℃ baking oven;
(4) colourless powder of drying was calcined 5 hours under 650 ℃, the black powder that obtains is ZnMnO 3Porous microsphere.
(5) by weight taking by weighing above-mentioned ZnMnO for the ratio of 8:1:25 3Porous microsphere, acetylene black and 2wt% sodium alginate soln are prepared into electrode slice and are assembled into button cell with the method for routine.

Claims (7)

1. lithium ion battery negative material ZnMnO 3Porous microsphere is characterized in that, described porous ZnMnO 3Microballoon makes by the following method:
(1) with soluble manganese salt and soluble zinc salt in molar ratio for 1:1 joins in the deionized water, stir, be made into the colourless solution that total amount of substance is 5～20mmol/10mL;
(2) mol ratio in sodium carbonate and the described soluble manganese salt of step (1) and zinc salt is the ratio of 1.0:1～2.0:1, adds sodium carbonate liquor in the described solution of step (1), stirs 20～40min, obtains white suspension;
(3) with step (2) gained white suspension suction filtration, water, ethanol are respectively washed 3～5 times again, obtain white powder, then white powder are dried in 80 ± 10 ℃ baking oven;
(4) colourless powder of drying was calcined 2～8 hours under 400～800 ℃, the black powder that obtains is ZnMnO 3Porous microsphere.
2. lithium ion battery negative material ZnMnO as claimed in claim 1 3Porous microsphere is characterized in that: the described soluble manganese salt of step (1) and soluble zinc salt are manganese acetate and zinc acetate or manganese nitrate and zinc nitrate.
3. lithium ion battery negative material ZnMnO as claimed in claim 1 3Porous microsphere is characterized in that: total amount of substance of the described soluble manganese salt of step (1) and soluble zinc salt is 8～12mmol/10mL.
4. lithium ion battery negative material ZnMnO as claimed in claim 1 3Porous microsphere is characterized in that: the mol ratio of the described sodium carbonate of step (2) and the described soluble manganese salt of step (1) and zinc salt is 1.05:1～1.2:1.
5. lithium ion battery negative material ZnMnO as claimed in claim 1 3Porous microsphere is characterized in that: the described calcining heat of step (5) is 500～700 ℃, and calcination time is 3～6 hours.
6. the described lithium ion battery negative material ZnMnO of claim 1 3The application of porous microsphere in the preparation lithium ion battery with high energy density.
7. application as claimed in claim 6 is characterized in that, the method for described application is: by weight taking by weighing ZnMnO for the ratio of 8:1:25 3Porous microsphere, acetylene black and 2wt% sodium alginate soln are prepared into electrode slice and are assembled into button cell with the method for routine.
CN2012104441292A 2012-11-08 2012-11-08 Lithium ion battery cathode material ZnMnO3 porous microsphere and application Pending CN102931389A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934592A (en) * 2015-05-18 2015-09-23 龙岩学院 Preparation method for anode material ZnMnO3 of lithium ion battery
CN109390564A (en) * 2017-08-03 2019-02-26 中国科学院苏州纳米技术与纳米仿生研究所 Ternary metal oxide, preparation method and application based on zinc ion doping
CN113206228A (en) * 2021-04-21 2021-08-03 华南师范大学 Zn-Mn bimetal lithium ion battery cathode material and preparation method thereof
CN113422048A (en) * 2021-06-23 2021-09-21 上海电力大学 Preparation method and application of novel water-based zinc ion battery positive electrode material
CN115709081A (en) * 2022-10-14 2023-02-24 华南师范大学 Solid solution porous microsphere, preparation method thereof and application of solid solution porous microsphere in photocatalytic hydrogen production

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CN102280642A (en) * 2011-07-07 2011-12-14 苏州大学 Application of alginate serving as adhesive in preparing electrode sheet

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934592A (en) * 2015-05-18 2015-09-23 龙岩学院 Preparation method for anode material ZnMnO3 of lithium ion battery
CN104934592B (en) * 2015-05-18 2018-12-07 龙岩学院 A kind of lithium ion battery negative material ZnMnO3Preparation method
CN109390564A (en) * 2017-08-03 2019-02-26 中国科学院苏州纳米技术与纳米仿生研究所 Ternary metal oxide, preparation method and application based on zinc ion doping
CN109390564B (en) * 2017-08-03 2020-08-28 中国科学院苏州纳米技术与纳米仿生研究所 Ternary metal oxide based on zinc ion doping, preparation method and application thereof
CN113206228A (en) * 2021-04-21 2021-08-03 华南师范大学 Zn-Mn bimetal lithium ion battery cathode material and preparation method thereof
CN113422048A (en) * 2021-06-23 2021-09-21 上海电力大学 Preparation method and application of novel water-based zinc ion battery positive electrode material
CN113422048B (en) * 2021-06-23 2022-04-01 上海电力大学 Preparation method and application of anode material of water-based zinc ion battery
CN115709081A (en) * 2022-10-14 2023-02-24 华南师范大学 Solid solution porous microsphere, preparation method thereof and application of solid solution porous microsphere in photocatalytic hydrogen production
CN115709081B (en) * 2022-10-14 2024-02-20 华南师范大学 Solid solution porous microsphere, preparation method thereof and application of solid solution porous microsphere in photocatalytic hydrogen production

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Application publication date: 20130213