CN102280640B - Novel anode material for lithium-ion secondary battery - Google Patents
Novel anode material for lithium-ion secondary battery Download PDFInfo
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- CN102280640B CN102280640B CN201110193049XA CN201110193049A CN102280640B CN 102280640 B CN102280640 B CN 102280640B CN 201110193049X A CN201110193049X A CN 201110193049XA CN 201110193049 A CN201110193049 A CN 201110193049A CN 102280640 B CN102280640 B CN 102280640B
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a novel anode material for a lithium-ion secondary battery. The anode material comprises transition metal carbonate which is prepared by a synthesis method, the anode material is used for preparing a pole piece of a battery cathode, and the method comprises the following steps of: 1) uniformly mixing the transition metal carbonate, a conductive agent and an adhesive to obtain a mixture; and 2) rolling the mixture into a piece, loading the piece on a current collector or directly coating the piece on the current collector to obtain the pole piece of the battery cathode. The invention has the advantages that: the anode material has higher heat stability and excellent electrochemical performance, and compared with anode materials of other lithium ion batteries, the anode material is rich in nature and has lower production cost than the other anode materials. Therefore, the anode material has wide application prospect in the field of lithium ion batteries.
Description
Technical field
The present invention relates to lithium ion battery electrode material and technology of preparing thereof, particularly a kind of Novel anode material for lithium rechargeable battery.
Background technology
The many merits such as lithium ion battery is high due to energy density, memory-less effect and good stability are considered to the secondary cell of tool development prospect, and are universal in the portable electric devices such as mobile phone, notebook computer and digital camera at present.In order to reduce energy crisis and environmental pollution, lithium ion battery begins to set foot in large-scale energy storage and power-equipment in recent years, the exploitation energy density high, have extended cycle life and the electrode material of the new type lithium ion battery that security performance is good extremely urgent.Negative material plays a key effect to the security performance of lithium ion battery.Common negative material mainly contains material with carbon element, Li-Ti oxide, tin-based material, silica-base material and transition metal oxide etc. at present.Material with carbon element and Li-Ti oxide all have good cyclical stability, but the specific capacity of material is lower; The volumetric expansion in charge and discharge process of tinbase and silica-base material causes the serious efflorescence of material, has destroyed the network of electric transmission, thereby has limited their practical application [Journal of Power Sources, 2011,196,13 – 24].Therefore the research emphasis that seek that specific capacity is relatively high, good cycling stability and the relatively cheap negative material of price becomes people.Carbonate content is abundant, low price, and existing multiple carbonate is widely applied in various aspects such as building, food processing and medical treatment at present, it is applied to the report of field of lithium ion secondary as electrode material but yet there are no so far.Transition metal is because having changeable chemical valence, and its compound can be used as electrode material, as lithium transition metal phosphates LiFePO
4Deng owing to having the advantages such as low price, Stability Analysis of Structures and security performance are good, be taken as lithium ion secondary battery anode material and be widely used [Energy Environ. Sci., 2011,4,805 – 817].This patent is studied as ion secondary battery cathode material lithium transition metal carbonate with the changeable characteristics of transition metal compound valency in conjunction with carbonate content is abundant, to improving the performance of lithium ion battery negative material.
Summary of the invention
The objective of the invention is for above-mentioned technical Analysis, a kind of Novel anode material for lithium rechargeable battery is provided, with the theory of transition metal carbonate as lithium ion battery negative material, to improve the performance of lithium ion battery negative material, accelerate the suitability for industrialized production process of lithium ion battery negative material.
Technical scheme of the present invention:
A kind of Novel anode material for lithium rechargeable battery comprises transition metal carbonate MCO
3
Described transition metal carbonate MCO
3Middle transition metal M is iron, cobalt, nickel, copper, zinc, manganese, chromium, molybdenum, vanadium, yttrium or cadmium.
Described transition metal carbonate adopts the synthetic method preparation, and described synthetic method comprises that hydro thermal method, Hydrolyze method, coprecipitation, urea high-pressure lixiviation process, carbon dioxide saturation, natural sediment method, chemical vapor deposition, thermalization study deposition or discharge decomposition method.
A kind of application of described Novel anode material for lithium rechargeable battery, step is as follows:
1) transition metal carbonate, conductive agent and binding agent is evenly mixed, obtain mixture;
2) be carried in flakes the said mixture roll extrusion on collector or directly be applied in and make negative pole piece of battery on collector.
Described conductive agent is acetylene black, superconduction carbon black, carbon fiber, Graphene, superconduction carbon black, cerium oxide, polyaniline, polypyrrole or polythiophene.
Described binding agent is polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC), polyethylene glycol (PVA) or butadiene styrene resin (SBR).
In described mixture, the quality percentage composition of each component is respectively: transition metal carbonate is 50 ~ 85%, and conductive agent is 30 ~ 10%, and binding agent is surplus.
Advantage of the present invention is: first the transition metal carbonate material is applied to the lithium ion battery industry, this material list reveals higher capacity and excellent cyclical stability, under 50 mA/g current densities, the initial charge capacity can reach 900mAh/g, after 30 weeks of circulation, capacity still can remain on 540 mAh/g, compare with conventional negative material, the transition metal carbonate material has more wide application prospect in field of lithium ion secondary.
Description of drawings
Fig. 1 is CoCO
3XRD figure.
Fig. 2 is CoCO
3SEM figure.
Fig. 3 is CoCO
3TG figure.
Fig. 4 is CoCO
3First three all charging and discharging curve figure.
Fig. 5 is CoCO
3The discharge cycles performance map.
Embodiment
The invention will be further described below in conjunction with example, but be not limited to this.
Embodiment 1:
A kind of Novel anode material for lithium rechargeable battery comprises cobalt carbonate, and cobalt carbonate adopts hydro thermal method synthetic, and step is: get cobalt acetate 0.75 g, urea 1.50 g, PVP 1.50 g, diethylene glycol (DEG) 60 mL, stir in water heating kettle, 200
oC hydro-thermal 16 h; Centrifuge washing, 150
oAfter the dry processing of C, can make cube shaped CoCO
3
Use this negative material and prepare electrode slice, step is as follows: 1) with CoCO
3, acetylene black and polytetrafluoroethylene be 75%, 15%, 10% ratio mixing in the quality percentage composition, is stirred to material binding and becomes one, and obtains doughy mix; 2) above-mentioned doughy mix thing is rolled into thickness on iron plate and is about 80 microns thin slices, then being cut into diameter is the circular electric pole piece of 8 mm.
With above-mentioned circular electric pole piece 100
oAfter C oven for drying 12 h, carry out the battery assembling.Take metal lithium sheet as to electrode and reference electrode.The electrolyte that adopts is that ethyl carbonate, carbonic acid Methylethyl ester, dimethyl carbonate volume ratio are that the mixed liquor of 1:1:1 is made solvent, LiPF
6Make solute, concentration is 1.0 mol/L, is assembled into simulated battery.0.01 ~ 3.0 V constant current charge-discharge under the battery room temperature of assembling, charging and discharging currents density is 50 mAh/g.
Fig. 1 is CoCO
3The XRD figure of material.The analysis showed that: this material belongs to orthorhombic system, R
The c space group.
Fig. 2 is the scanning electron microscope (SEM) photograph of this material.As figure shows, this material is micron-sized cube.
Fig. 3 is the thermogravimetric curve figure of this material.Show in figure: 300
oC material in the past is to stablize very much, is conducive to keep it as the stability of electrode material.
Fig. 4 is first three all charging and discharging curve of this material.Test condition is: current density 50 mA/g, voltage range 0.01 ~ 3 V.Show in figure: the charge/discharge capacity in the first week is respectively 940 mAh/g and 1580 mAh/g, and the formation of electrode and electrolyte interface generation side reaction and Solid phase electrolysis liquid interfacial film is the main cause that causes larger irreversible capacity.
Fig. 5 is that this material is that 50 mA/g, voltage range are the cycle performance figure of 0.01 ~ 3 V in current density.Show in figure: along with the carrying out of circulation, the capacity of material begins slowly to decay, but the capacity that is circulated to the 30th all materials still can remain on 540 mAh/g, shows that this material has broad application prospects.
Embodiment 2:
A kind of Novel anode material for lithium rechargeable battery comprises nickelous carbonate, and nickelous carbonate adopts the natural sediment method synthetic, and step is: get NiSO
46H
2O 1.314 g, CTAB 0.05 g, Li
2CO
30.50 g is dissolved in 40 mL distilled water, stirs in 100 mL beakers, and 60
oC hydro-thermal 12 h; Centrifuge washing, the dry processing; 200
oC heating 2 h obtain pure phase NiCO
3
Use this negative material and prepare electrode slice, step is as follows: 1) with NiCO
3, superconduction carbon black and Kynoar (PVDF) be 80%, 15%, 5% ratio mixing in the quality percentage composition, is stirred to the doughy mix that material binding becomes one; 2) above-mentioned doughy mix is rolled on iron plate is about the thin slice of 80 microns, then being cut into diameter is the circular electric pole piece of 8 mm.
With above-mentioned pole piece 100
oAfter C oven for drying 12 h, carry out the battery assembling.Take metal lithium sheet as to electrode and reference electrode.The electrolyte that adopts is that ethyl carbonate, carbonic acid Methylethyl ester, dimethyl carbonate volume ratio are that the mixed liquor of 1:1:1 is made solvent, LiPF
6Make solute, concentration is 1.0 mol/L, is assembled into simulated battery.0.01 ~ 3.0 V constant current charge-discharge under the battery room temperature of assembling, charging and discharging currents density is 50 mAh/g.
Test result shows: first all charge/discharge capacity are respectively 1059 and 1754 mAh/g, more than after 30 weeks of circulation, capacity still keeps 400 mAh/g.Material list has revealed higher energy storage potentiality.
Embodiment 3:
A kind of Novel anode material for lithium rechargeable battery comprises ferric carbonate, and ferric carbonate adopts hydro thermal method synthetic, and step is: get FeCl
36H
2O 0.541 g, ascorbic acid 1.8 g, Na
2CO
30.875 g, glucose 0.416 g are dissolved in 40 mL distilled water, stir in 50 mL water heating kettles, and 140
oC hydro-thermal 12 h.Centrifuge washing, the dry processing obtains pure phase FeCO
3
Use this negative material and prepare electrode slice, step is as follows: 1) with FeCO
3, superconduction carbon black and sodium carboxymethylcellulose (CMC) be 60%, 25%, 15% ratio mixing in the quality percentage composition, is stirred to the doughy mix that material binding becomes one; 2) above-mentioned doughy mix is rolled on iron plate is about 80 microns thin slices, then being cut into diameter is the circular electric pole piece of 8 mm.
With above-mentioned pole piece 100
oAfter C oven for drying 12 h, carry out the battery assembling.Take metal lithium sheet as to electrode and reference electrode.The electrolyte that adopts is that ethyl carbonate, carbonic acid Methylethyl ester, dimethyl carbonate volume ratio are that the mixed liquor of 1:1:1 is made solvent, LiPF
6Make solute, concentration is 1.0 mol/L, is assembled into simulated battery.0.01 ~ 3.0 V constant current charge-discharge under the battery room temperature of assembling, charging and discharging currents density is 50 mAh/g.
Test result shows: FeCO
3First all charge/discharge capacity are respectively 852 and 1460 mAh/g, more than after 30 weeks of circulation, capacity still keeps 420 mAh/g.Material list has revealed higher energy storage potentiality.
Embodiment 4:
A kind of Novel anode material for lithium rechargeable battery comprises manganese carbonate, and manganese carbonate adopts hydro thermal method synthetic, and step is: MnCO
3Synthetic: get MnSO
46H
2O 1.026 g, CTAB 0.05 g, Li
2CO
30.50 g is dissolved in 40 mL distilled water, stirs in 50 mL water heating kettles, and 140
oC hydro-thermal 12 h, centrifuge washing, the dry processing obtains pure phase MnCO
3
Use this negative material and prepare electrode slice, step is as follows: 1) with MnCO
3, polypyrrole and polyethylene glycol (PVA) be 70%, 20%, 10% ratio mixing in the quality percentage composition, is stirred to the doughy mix that material binding becomes one; 2) above-mentioned doughy mix is rolled on iron plate is about 80 microns thin slices, then being cut into diameter is the circular electric pole piece of 8 mm.
With above-mentioned pole piece 100
oAfter C oven for drying 12 h, carry out the battery assembling.Take metal lithium sheet as to electrode and reference electrode.The electrolyte that adopts is that ethyl carbonate, carbonic acid Methylethyl ester, dimethyl carbonate volume ratio are that the mixed liquor of 1:1:1 is made solvent, LiPF
6Make solute, concentration is 1.0 mol/L, is assembled into simulated battery.0.01 ~ 3.0 V constant current charge-discharge under the battery room temperature of assembling, charging and discharging currents density is 50 mAh/g.
Test result shows: first all charge/discharge capacity are respectively 968 and 1984 mAh/g, more than after 30 weeks of circulation, capacity still keeps 450 mAh/g.Material list has revealed higher energy storage potentiality.
Claims (1)
1. application that is used for the negative material of lithium rechargeable battery, described negative material is CoCO
3, CoCO
3The employing hydro thermal method is synthetic, it is characterized in that: for the preparation of negative pole piece of battery and be assembled into simulated battery, step is as follows:
1) get cobalt acetate 0.75g, urea 1.50g, PVP1.50g, diethylene glycol (DEG) 60mL, stir in water heating kettle, 200 ℃ of hydro-thermal 16h; Centrifuge washing after 150 ℃ of dry processing, can make cube shaped CoCO
3
2) with CoCO
3, acetylene black and polytetrafluoroethylene be 75%, 15%, 10% ratio mixing in the quality percentage composition, is stirred to material binding and becomes one, and obtains doughy mix;
3) above-mentioned doughy mix being rolled into thickness on iron plate is 80 microns thin slices, and then being cut into diameter is the circular electric pole piece of 8mm;
4) with above-mentioned circular electric pole piece after 100 ℃ of oven for drying 12h, carry out the battery assembling, take metal lithium sheet as to electrode and reference electrode, the electrolyte of employing is that ethyl carbonate, carbonic acid Methylethyl ester, dimethyl carbonate volume ratio are that the mixed liquor of 1: 1: 1 is made solvent, LiPF
6Make solute, concentration is 1.0mol/L, is assembled into simulated battery.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413941B (en) * | 2013-07-23 | 2015-12-23 | 华南农业大学 | A kind of lithium ion battery cathode material and its preparation method |
| CN103840132B (en) * | 2014-03-03 | 2016-08-17 | 湖南雅城新材料股份有限公司 | Ferrous carbonate/graphene composite material and its preparation method and application |
| CN103887487A (en) * | 2014-04-15 | 2014-06-25 | 山东大学 | Dumbbell cobalt carbonate material and application thereof |
| CN104157838A (en) * | 2014-08-27 | 2014-11-19 | 山东大学 | Cobalt carbonate-polypyrrole composite anode material used for power lithium ion battery and preparation method thereof |
| CN104556237B (en) * | 2014-12-08 | 2017-04-19 | 中国科学院合肥物质科学研究院 | Ferrous carbonate hexahedron and preparation method thereof |
| CN105489860A (en) * | 2015-12-15 | 2016-04-13 | 昆明仁旺科技有限公司 | Anode material for lithium-ion battery and preparation method of anode material |
| CN105506784A (en) * | 2016-02-05 | 2016-04-20 | 扬州大学 | Preparation method of composite carbon nanofibers with high specific surface area |
| CN106450236B (en) * | 2016-12-07 | 2019-02-05 | 清华大学深圳研究生院 | A kind of preparation method of lithium ion battery negative material |
| CN107317019B (en) * | 2017-08-02 | 2020-03-31 | 中国石油大学(华东) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof |
| CN108666552B (en) * | 2018-05-02 | 2020-05-19 | 清华大学 | Calcium-manganese carbonate composite material and preparation method and application thereof |
| CN110690447B (en) * | 2019-10-15 | 2021-08-27 | 合肥国轩高科动力能源有限公司 | Ternary cathode material and preparation method and application thereof |
| CN111024681B (en) * | 2019-12-17 | 2023-01-17 | 国联汽车动力电池研究院有限责任公司 | Ternary lithium ion battery positive pole piece analysis method |
| CN113788516B (en) * | 2021-09-27 | 2022-09-06 | 江南大学 | Application of transition metal carbonate nano material in electrocatalytic reduction reaction of nitrate |
| CN114478958B (en) * | 2022-01-07 | 2023-08-29 | 瑞红锂电池材料(苏州)有限公司 | Modified SBR binder and preparation method and application thereof |
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| CN101325253A (en) * | 2007-06-13 | 2008-12-17 | 中国科学院金属研究所 | Method for preparing cathode material for high capacity lithium ion battery |
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