CN103094561B - Preparation method of lithium-containing lead oxide energy storage material - Google Patents
Preparation method of lithium-containing lead oxide energy storage material Download PDFInfo
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- CN103094561B CN103094561B CN201310031351.4A CN201310031351A CN103094561B CN 103094561 B CN103094561 B CN 103094561B CN 201310031351 A CN201310031351 A CN 201310031351A CN 103094561 B CN103094561 B CN 103094561B
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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 preparation method of a lithium-contained lead oxide energy storage material. The preparation method comprises the following steps of: combining the carbon source, the lithium source and the lead source in secondary water and stoving directly in a drying oven for 5-10 hours at the temperature of 60-160 DEG C; then calcining the prepared solid products for 1-18 hours at the temperature of 600-900 DEG C and cooling to room temperature to obtain the lead oxide energy storage material containing lithium. The raw material used in the preparation method is low-priced and easy to get, the process is easy to apply, and gas which pollutes the environment is not generated in the process, and the lithium-containing lead oxide energy storage material prepared by the invention has a normal charge and discharge performance and a stable product performance, is lithium ion energy storage active material with application potentials, and is expected to become the active material of lithium ion secondary battery, thereby having higher commercial values.
Description
Technical field
The preparation method who the present invention relates to a kind of lead oxides energy storage material containing lithium, belongs to energy and material technical field.
Background technology
At present, relatively ripe lithium rechargeable battery active material mainly contains LiCoO
2, LiMn
2o
4, LiFePO
4, LiNiO
2etc., to find through long-term research, above each energy storage material has different pluses and minuses, as LiCoO
2chemical property is good, but expensive; LiMn
2o
4price is low, but poor performance; LiFePO
4moderate cost, but batch production is unstable, etc.In order to improve the performance of different materials, researchers are improving the material shortcoming while separately, are also making great efforts seeking better substitution material.Lead oxides especially brown lead oxide is widely used as positive electrode in traditional lead acid accumulator.Lead oxides and lithium niobate (theoretical specific capacity of plumbic acid lithium is 99.8mAh/g) structure containing lithium approach, although degree of crystallinity is lower, order is waited to improve, and the invertibity of lithium ion electrochemistry deintercalation process is therein high.This kind has the advantages such as preparation cost is cheap, safe, production technology is simple, cyclicity is good containing lithium lead oxides, the energy storage material that likely becomes type lithium ion is widely used, by suitable improvement in performance, likely become lithium rechargeable battery active material.But investigation shows, has no lithium ion and lead oxide are combined, and is prepared into the report of the energy storage material of accurate plumbic acid lithium.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the lead oxides energy storage material containing lithium.By the sign to product and test, find that this lead oxides energy storage material that contains lithium has metastable charge-discharge performance and capacity, be a kind of potential energy storage material and secondary cell active material.
It is as follows that the present invention solves the technical scheme that its technical problem takes: a kind of preparation method of the lead oxides energy storage material containing lithium, comprises the following steps:
(1) raw material premix
Carbon source, lithium source, plumbous source and redistilled water are pressed to (2～5): (1～6): (1～2): the amount of substance of (80～120) is than mixing;
(2) dry
Mixture is dried in baking oven to 5～10 hours time in 60～160 DEG C;
(3) roasting, compressing tablet
Desciccate is placed in to high temperature furnace, in 250～450 DEG C of constant temperature calcining 3-5h, is cooled to after room temperature, the powder obtaining is pressed into sheet;
(4) calcining
The chip solid product that step (3) is obtained is placed in the reactor of sealing, and roasting 1～18 hour between 600～900 DEG C obtains the lead oxides energy storage material containing lithium after pulverizing, grinding;
In described preparation method, carbon source is selected from one or more in carbon black, acetylene black, graphite, glucose, cyclodextrin;
Lithium source is one or more in lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxalate, lithium acetate, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate and lithium chloride;
Plumbous source is selected from one or more in plumbi nitras, lead phosphate, ceruse;
In described preparation method, when carbon source, He Qian source, lithium source are mixed in intermediate water, magnetic agitation is fully mixed for 2～6 hours.
The beneficial effect that the present invention obtains is as follows: (1) does not have pernicious gas or other to have the air release of penetrating odor in whole preparation process, simplifies production equipment, reduces production costs; (2) what the present invention prepared have containing the lead oxides energy storage material of lithium, and to be similar to performance and the properties of product of secondary cell active material stable; (3) the present invention be by lithium ion and lead oxide the two in conjunction with the new energy storage material of preparing.Although this invention product capacity is lower, applicable to suitable accumulate energy storage field, the advantage such as this product processes possesses that equipment investment is few simultaneously, technological process simplification, cost of material are cheap, easily realizes suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the figure of the X-ray diffraction (XRD) containing the lead oxides of lithium prepared by embodiment 1.
Fig. 2 is the figure of the scanning electron microscopy (SEM) containing the lead oxides of lithium prepared by embodiment 1.
Fig. 3 is the charging and discharging curve under 0.1C multiplying power containing the lead oxides of lithium prepared by embodiment 1.
Embodiment
Following examples are used for illustrating the present invention.
Embodiment 1
3.31g plumbi nitras, 0.24g glucose and 0.72g lithium hydroxide are mixed in redistilled water.Mix products is placed in air dry oven, dry with 150 DEG C.Desciccate is placed in to high temperature furnace, heat up in 300 DEG C of constant temperature calcining 3h with the 14 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, after making powder, carry out compressing tablet, sheet is placed in to high temperature furnace again, heat up in 700 DEG C of constant temperature calcining 5h with the 14 DEG C/min rate of heat addition, product makes containing lithium lead oxides powder after grinding.Fig. 1 X-ray diffraction analysis result shows, preparedly in spectrogram, has impurity peaks containing not relatively regular structure of lithium lead oxides powder, and product purity is not high.Fig. 2 amplifies the electron micrograph of 30,000 times containing lithium lead oxides powder, product is sheet, and structurally ordered property is poor.
Take that 0.8g makes containing lithium lead oxides powder, add 0.1g acetylene black and 0.1g to be dissolved in Kynoar (PVDF) binding agent of N-N' dimethyl pyrrolidone, after mixing, be applied to and on aluminium foil, make positive plate.In nitrogen atmosphere dry glove box, taking metal lithium sheet as to electrode, Celgard2400 is barrier film, ethylene carbonate (EC)+ethylene carbonate methyl esters (EMC)+ethyl acetate (EA)+1molL
-1liPF
6for electrolyte, be assembled into battery.
In 1.50V-3.50V voltage range, battery is carried out to charge and discharge cycles experiment.Accompanying drawing 3 is 0.1C multiplying power battery charging and discharging curve.As seen from Figure 3, it is 1.40-1.45V that the present invention makes containing lithium lead oxides material discharging voltage, and reversible specific capacity reaches 43.5mAh/g, is 43.4% of theoretical specific capacity.Cycle performance of battery is also relatively stable, with the charging of 0.2C multiplying power, through 20 not obviously decay of cycle battery capacity.
Embodiment 2
3.10g plumbi nitras, 0.24g glucose and 0.84g lithium hydroxide are mixed in intermediate water.Mix products is placed in air dry oven, dry with 100 DEG C.Heat up in 350 DEG C of constant temperature calcining 3h with the 10 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, after making powder, carry out compressing tablet, this product is placed in to high temperature furnace, heat up in 750 DEG C of calcining at constant temperature 14h with the 14 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, make containing lithium lead oxides powder.It is 1.51-1.55V that the present invention makes containing lithium lead oxides material discharging voltage, and reversible specific capacity is up to 41.3mAh/g.With 0.1C rate charge-discharge, do not decay through 30 cycle battery capacity.
Embodiment 3
3.23g plumbi nitras, 0.5g glucose, 0.84g lithium hydroxide and 5.5g citric acid are mixed in intermediate water.Mix products is placed in air dry oven, dry with 100 DEG C.Desciccate is placed in to high temperature furnace, heat up in 300 DEG C of constant temperature calcining 3h with the 14 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, after making powder, carry out compressing tablet, sheet is placed in to high temperature furnace again, heat up in 700 DEG C of constant temperature calcining 7h with the 14 DEG C/min rate of heat addition, product makes containing lithium lead oxides powder after grinding.It is 1.47-1.50V that the present invention makes containing lithium lead oxides material charging/discharging voltage, and reversible specific capacity is up to 33.3mAh/g.With 0.2C rate charge-discharge, do not decay through 20 cycle battery capacity.
Embodiment 4
4.965g plumbi nitras, 0.45g glucose, 1.04g lithium hydroxide are mixed in intermediate water.Mix products is placed in air dry oven, dry with 110 DEG C.Heat up in 380 DEG C of constant temperature calcining 2h with the 12 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, after making powder, carry out compressing tablet, this product is placed in to high temperature furnace, heat up in 800 DEG C of constant temperature calcining 6h with the 14 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, make containing lithium lead oxides powder.It is 1.50-1.53V that the present invention makes containing lithium lead oxides material discharging voltage, and reversible specific capacity is up to 34.4mAh/g.With 0.2C rate charge-discharge, do not decay through 15 cycle battery capacity.
Embodiment 5
4.8g ceruse, 0.8g glucose, 1.04g lithium hydroxide are mixed in intermediate water.Mix products is placed in air dry oven, dry with 95 DEG C.Desciccate is placed in to high temperature furnace to heat up in 300 DEG C of constant temperature calcining 3h with the 14 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, after making powder, carry out compressing tablet, product is placed in to high temperature furnace again, heat up in 750 DEG C of constant temperature calcining 7h with the 14 DEG C/min rate of heat addition, product makes containing lithium lead oxides powder after grinding.It is 1.32-1.35V that the present invention makes product discharge voltage, and reversible specific capacity is up to 30.6mAh/g.With 0.2C rate charge-discharge, do not decay through 15 cycle battery capacity.
Embodiment 6
3.00g lead phosphate, 0.5g glucose, 0.84g lithium hydroxide and 2g citric acid are mixed in intermediate water.Mix products is placed in air dry oven, dry with 95 DEG C.Heat up in 300 DEG C of constant temperature calcining 2h with the 15 DEG C/min rate of heat addition, then be cooled to room temperature with 20 DEG C/min cooling rate, after making powder, carry out compressing tablet, this product is placed in to high temperature furnace, heat up in 850 DEG C of calcining at constant temperature 6h with the 14 DEG C/min rate of heat addition, then be cooled to room temperature with 10 DEG C/min cooling rate, make containing lithium lead oxides powder.It is 1.30-1.35V that the present invention makes containing lithium lead oxides material discharging voltage, and reversible specific capacity is up to 33.4mAh/g.With 0.2C rate charge-discharge, do not decay through 10 cycle battery capacity.
Claims (2)
1. a preparation method who contains the lead oxides energy storage material of lithium, is characterized in that comprising the following steps:
(1) raw material premix
Carbon source, lithium source, plumbous source and redistilled water are pressed to (2～5): (1～6): (1～2): the ratio of the amount of substance of (80～120) mixes;
Wherein, carbon source is selected from one or more in carbon black, acetylene black, graphite, glucose, cyclodextrin;
Lithium source is one or more in lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxalate, lithium acetate, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate and lithium chloride;
Plumbous source is selected from one or more in plumbi nitras, lead phosphate, ceruse;
(2) dry
Mixture is dried in baking oven to 5～10 hours time in 60～160 DEG C;
(3) roasting, compressing tablet
Desciccate is placed in to high temperature furnace, in 250～450 DEG C of constant temperature calcining 3-5h, is cooled to after room temperature, the powder obtaining is pressed into sheet;
(4) calcining
The chip solid product that step (3) is obtained is placed in the reactor of sealing, and roasting 1～18 hour between 600～900 DEG C obtains the lead oxides energy storage material containing lithium after pulverizing, grinding.
2. preparation method according to claim 1, while it is characterized in that carbon source, He Qian source, lithium source to mix in intermediate water, magnetic agitation is fully mixed for 2～6 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101504980A (en) * | 2008-02-07 | 2009-08-12 | 信越化学工业株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, making method, lithium ion secondary battery, and electrochemical capacitor |
| CN101993054A (en) * | 2010-11-17 | 2011-03-30 | 河北师范大学 | Method for preparing lithium ion phosphate material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101504980A (en) * | 2008-02-07 | 2009-08-12 | 信越化学工业株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, making method, lithium ion secondary battery, and electrochemical capacitor |
| CN101993054A (en) * | 2010-11-17 | 2011-03-30 | 河北师范大学 | Method for preparing lithium ion phosphate material |
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