CN102983325B - The preparation method of positive electrode laminated cell lithium manganate of lithium ion - Google Patents
The preparation method of positive electrode laminated cell lithium manganate of lithium ion Download PDFInfo
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Abstract
The invention belongs to field of lithium ion battery material preparation, relate to the preparation method of positive electrode laminated cell lithium manganate of lithium ion.Described method comprise by manganese powder and Aqueous Lithium Salts according to 1: 3 ~ 30 solid-liquid mass ratio mix, introduce complexing agent ammonium radical ion as reaction controlling agent, the mixed reaction solution obtained is stirred under normal pressure and reacts, reaction temperature controls at 50 DEG C ~ 100 DEG C, reaction continues 5h ~ 60h, after having reacted, product is carried out suction filtration, after suction filtration, gained solid product is through deionized water washing and drying, obtains positive electrode stratiform LiMn2O4.The positive electrode of the inventive method synthesis has that purity is high, electrochemistry capacitance is large and the advantage such as high-energy-density, and the synthetic route of the inventive method is simple, mild condition, low for equipment requirements, with low cost, is easy to realize large-scale industrial production.
Description
Technical field
The invention belongs to field of lithium ion battery material preparation, be specifically related to the soft chemical preparation process of atmospheric low-temperature of lithium ion secondary battery anode material layered lithium manganate.
Background technology
Positive electrode determines performance and the price of lithium rechargeable battery to a great extent.At present, business-like lithium ion secondary battery anode material is cobalt acid lithium mainly, but due to the poisonous and scarcity of resources of cobalt element, cause cobalt acid lithium can cause severe contamination to environment and price is very expensive, thus the lithium rechargeable battery that to make with cobalt acid lithium be positive electrode is difficult to apply more on a large scale.Therefore, outstanding chemical property, better fail safe is sought to have and the new type lithium ion secondary battery positive electrode material of environmentally safe seems most important to the industry development of lithium electricity.
The theoretical capacity of layered lithium manganate has 285mAhg
-1, actual capacity is more than 200mAhg
-1, have that fail safe is good, aboundresources, the advantage that cheap, toxicity is little, be considered to one of best substitution material of cobalt acid lithium, its major defect is preparation difficulty.The preparation method of current layered lithium manganate mainly contains high-temperature solid phase reaction method, sol-gal process, hydro thermal method, ion-exchange etc., but these methods all also exist weak point.
US5747194A american documentation literature (USE OF A STABLE FORM LiMnO
2aS CATHODE IN LITHIUM CELL) in disclose following content: by β-MnO
2and Li
2cO
3be after 2: 1 mixed pressuring plates in mass ratio, in argon gas atmosphere prior to 600 DEG C of preliminary treatment two hours to remove CO
2, then at 800 DEG C ~ 900 DEG C Gap response 3 days at twice, obtain rhombic system layered lithium manganate.Article (En Mei Jin, Bo Jinb, Yeon-Su Jeon, the et al.Electrochemical properties of LiMnO that the people such as Jin deliver
2in propose with Mn for lithium polymer battery [J] .Journal of Power Sources, 2009,189: 620-623.)
3o
4and LiOHH
2o is raw material, and in 1050 DEG C of calcinings 15 hours after mixed pressuring plate, calcined product through Quenching in liquid nitrogen and ball milling after 10 hours, obtains rhombic system layered lithium manganate.Electrochemical property test (2.0V to 4.3V, 0.2mAcm
-2) show its first discharge capacity be 62mAhg
-1, after 70 circulations, discharge capacity is 124mAhg
-1.High-temperature solid phase reaction method needs high-temperature service, and the reaction time is long, needs atmosphere protection in course of reaction, and the shortcoming such as product exists consistency difference, and initial discharge specific capacity is low.
Disclose following content in CN1553529A Chinese patent literature (the oxidized inserting layer preparation method of positive electrode laminated cell lithium manganate of lithium ion): be dissolved in the deionized water boiled under nitrogen protection respectively by manganese salt and highly basic, preparation has the manganous hydroxide Mn (OH) of layer structure
2precursor material, joins in stratiform object suspension-turbid liquid by a certain percentage by lithium compound intercalated object, carry out intercalation and obtain layered lithium manganate under the synergy of oxidant.Electrochemical property test shows, its first reversible capacity can reach 200mAhg
-1.The layered lithium manganate product chemical property that the method obtains is better, but preparation process is complicated, needs Moist chemical synthesis in two steps, and Mn (OH)
2need in precursor material preparation process to boil deionized water and lead to nitrogen protection to remove the dissolved oxygen in solution, condition is harsh.
CN1674322A Chinese patent literature (positive electrode material of lithium secondary cell-rhombic system LiMnO
2preparation method) in disclose following content: be that the compound of the bivalent manganese of 1: 1: 7.5 ~ 30, manganese dioxide and lithium hydroxide are dissolved in distilled water by mol ratio, stir 4 ~ 6 hours in air at room temperature, then autoclave is loaded, isothermal reaction 5 ~ 7 days at 170 ~ 230 DEG C, neutral to pH value with rare oxalic acid cleaning after going out still, then by distilled water or washed with de-ionized water, oven dry of finally being anhydrated by sediment, namely obtains rhombic system LiMnO
2powder.The shortcoming of the method is course of reaction is HTHP, and condition is harsh, and reaction process is longer for cycle time, and autoclave equipment manufacturing cost is high, and material preparation cost is high.
Following content is disclosed: take electrolytic manganese dioxide as raw material in CN102249341A Chinese patent literature (a kind of layered lithium manganate cathode material for lithium ion battery manufacture method), at high temperature calcine, obtain manganese sesquioxide managnic oxide, manganese sesquioxide managnic oxide and natrium carbonicum calcinatum are mixed according to mol ratio 1: 1, then sinter, obtain NaMnO
2, take lithium source and NaMnO according to mol ratio 6 ~ 10: 1
2, filtered by reacted mixed liquor, sediment is layered lithium manganate after washing and drying.Electrochemical property test shows, its charging capacity is greater than 200mAhg
-1, discharge capacity is greater than 180mAhg
-1.The layered lithium manganate product chemical property that the method obtains is better, but preparation process is complicated, needs to obtain NaMnO through twice high-temperature burning process
2presoma carries out ion-exchange again, and whole preparation process flow process is complicated, the time is long, energy consumption is high.
Though above method is feasible technically, but in product quality, economic benefit or environmental protection etc., all there is certain problem, therefore, seek that technique is easier, condition milder, product quality are more excellent and the layered lithium manganate method for preparing anode material more friendly to environment is current lithium battery material preparation field is badly in need of a major issue solving.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides that a kind of synthetic route is simple, mild condition, with low cost, obtained target product excellent performance and be easy to realize the preparation method of the positive electrode laminated cell lithium manganate of lithium ion of large-scale industrial production.
For solving the problems of the technologies described above, the present invention proposes a kind of preparation method of positive electrode laminated cell lithium manganate of lithium ion, comprises the following steps:
By manganese powder and Aqueous Lithium Salts according to 1: 3 ~ 30 solid-liquid mass ratio mix, introduce complexing agent ammonium radical ion as reaction controlling agent (can add continuously in reactor disposable adding in reactor or when reaction is carried out when reacting batching), the mixed reaction solution obtained is stirred under normal pressure and reacts, reaction temperature controls at 50 DEG C ~ 100 DEG C, reaction continues 5h ~ 60h, after having reacted, product is carried out suction filtration, after suction filtration, gained solid product is through deionized water washing and drying, obtains positive electrode stratiform LiMn2O4.
In said method, preferably, described Aqueous Lithium Salts, containing one or more in lithium hydroxide, lithium chloride, lithium nitrate, lithium acetate, more preferably contains lithium hydroxide.In aforementioned preferred technical scheme, the preferred 1mol/L ~ 10mol/L of the concentration of lithium ion, more preferably 2mol/L ~ 8mol/L in described Aqueous Lithium Salts; Preferred 1mol/L ~ the 10mol/L of concentration of hydroxide ion, more preferably 2mol/L ~ 6mol/L.
In said method, described ammonium radical ion derive from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonia, ammoniacal liquor one or more; Preferred 0.01mol/L ~ the 2mol/L of the concentration of described ammonium radical ion in mixed reaction solution, more preferably 0.05mol/L ~ 1mol/L.
In said method, the solid matter with deionized water washing after described suction filtration is until washing lotion pH value is 7 ~ 14.
In said method, described dry time baking temperature preferably 100 DEG C ~ 120 DEG C, drying time preferred 10h ~ 20h.
In the present invention after suction filtration after the filtrate of gained and deionized water washing the washing lotion of gained recyclable after continue to use.
Compared with prior art, the invention has the advantages that:
(1) the rhombic system layered lithium manganate powder positive electrode of the inventive method synthesis have that purity is high, the advantage such as the large and high-energy-density of electrochemistry capacitance.
(2) raw material electrolytic metal manganese powder of the present invention and lithium salts cheap and easy to get, do not need in course of reaction to pass into protective gas, and reaction be operate at ambient pressure.
(3) synthetic route of the inventive method is simple, preparation condition is gentle, low for equipment requirements and with low cost, be easy to realize large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of rhombic system layered lithium manganate powder prepared by the embodiment of the present invention 1 and embodiment 2.
Fig. 2 is the first charge-discharge curve chart of electro-chemical test in the embodiment of the present invention 1.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described.
embodiment 1:
A preparation method for positive electrode laminated cell lithium manganate of lithium ion of the present invention, comprises the following steps:
Chelating agent ammonium chloride being added concentration is form mixed solution in the lithium hydroxide aqueous solution of 6mol/L, and the concentration of ammonium radical ion is 0.2mol/L.Mixed solution is pumped in open type atmospheric agitation reactor and be heated to 85 DEG C, then in reactor, electrolytic metal manganese powder is added, the mass ratio of manganese powder and lithium hydroxide aqueous solution is 1: 30, isothermal reaction 36 hours at 85 DEG C again, after having reacted, product is carried out suction filtration, the solid matter with deionized water washing obtained after suction filtration is 11.5 to pH value, and then dry 12h at 120 DEG C, obtains end product (i.e. target product).
The end product obtained to the method carries out XRD test, and as shown in Figure 1, this product belongs to rhombic system layered lithium manganate structure, and what ICP test result showed this product consists of Li
0.96mnO
2.As can be seen here, the inventive method has successfully prepared rhombic system layered lithium manganate positive electrode.The Electrochemical results of the present embodiment manganate cathode material for lithium as shown in Figure 2, as seen from Figure 2 in the charging/discharging voltage scope of 2.0V ~ 4.5V, with 15mAg
-1during current density first charge-discharge, initial charge capacity is 220mAhg
-1, discharge capacity is 194mAhg first
-1.
embodiment 2:
Added by chelating agent ammoniacal liquor in the mixed aqueous solution of lithium hydroxide and lithium chloride, wherein lithium concentration is 5mol/L, and hydroxide ion concentration is 4mol/L, and ammonium ion concentration is 0.1mol/L.Mixed solution is pumped in open type atmospheric agitation reactor and be heated to 85 DEG C, then in reactor, electrolytic metal manganese powder is added, the mass ratio of manganese powder and Aqueous Lithium Salts is 1: 20, by the isothermal reaction 30 hours at 85 DEG C of the mixed reaction solution that obtains, after having reacted, product is carried out suction filtration, the solid matter with deionized water washing obtained after suction filtration is 10.5 to washing lotion pH value, and then dry 15h at 120 DEG C, obtains end product (i.e. target product).
The end product obtained to said method carries out XRD test, and as shown in Figure 1, this product belongs to rhombic system layered lithium manganate structure, and what ICP test result showed this product consists of Li
0.94mnO
2.Show thus, the inventive method has successfully prepared rhombic system layered lithium manganate positive electrode.The Electrochemical results of the present embodiment manganate cathode material for lithium shows, within the scope of the charging/discharging voltage of 2.0V ~ 4.5V, with 15mAg
-1during current density discharge and recharge, initial charge capacity is 207mAhg
-1, discharge capacity is 181mAhg
-1, after 10 circulations, capacity still keeps 90% of initial capacity.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It is noted that for those skilled in the art, improvements and modifications without departing from the principles of the present invention, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a preparation method for positive electrode laminated cell lithium manganate of lithium ion, comprises the following steps:
By manganese powder and Aqueous Lithium Salts according to 1: 3 ~ 30 solid-liquid mass ratio mix, introduce complexing agent ammonium radical ion as reaction controlling agent, the mixed reaction solution obtained is stirred under normal pressure and reacts, reaction temperature controls at 50 DEG C ~ 100 DEG C, reaction continues 5h ~ 60h, after having reacted, product is carried out suction filtration, after suction filtration, gained solid product is through deionized water washing and drying, obtains positive electrode stratiform LiMn2O4;
Described ammonium radical ion derive from ammonia, ammoniacal liquor one or more; The concentration of described ammonium radical ion in mixed reaction solution is 0.01mol/L ~ 2mol/L.
2. the preparation method of positive electrode laminated cell lithium manganate of lithium ion according to claim 1, is characterized in that, described Aqueous Lithium Salts is containing one or more in lithium hydroxide, lithium chloride, lithium nitrate, lithium acetate.
3. the preparation method of positive electrode laminated cell lithium manganate of lithium ion according to claim 2, is characterized in that, described Aqueous Lithium Salts is containing lithium hydroxide.
4. the preparation method of positive electrode laminated cell lithium manganate of lithium ion according to claim 3, is characterized in that, in described Aqueous Lithium Salts, the concentration of lithium ion is 1mol/L ~ 10mol/L, and the concentration of hydroxide ion is 1mol/L ~ 10mol/L.
5. the preparation method of the positive electrode laminated cell lithium manganate of lithium ion according to any one of Claims 1 to 4, is characterized in that, the solid matter with deionized water washing after described suction filtration is until washing lotion pH value is 7 ~ 14.
6. the preparation method of the positive electrode laminated cell lithium manganate of lithium ion according to any one of Claims 1 to 4, is characterized in that, baking temperature during described drying is 100 DEG C ~ 120 DEG C, and drying time is 10h ~ 20h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1553529A (en) * | 2003-05-27 | 2004-12-08 | 北京化工大学 | Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode |
| CN101072731A (en) * | 2004-10-01 | 2007-11-14 | Cvrd英科有限公司 | Process for producing lithium transition metal oxides |
| CN101967013A (en) * | 2010-11-04 | 2011-02-09 | 中信大锰矿业有限责任公司 | Method for preparing high-purity lithium ion battery anode material such as lithium manganate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1553529A (en) * | 2003-05-27 | 2004-12-08 | 北京化工大学 | Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode |
| CN101072731A (en) * | 2004-10-01 | 2007-11-14 | Cvrd英科有限公司 | Process for producing lithium transition metal oxides |
| CN101967013A (en) * | 2010-11-04 | 2011-02-09 | 中信大锰矿业有限责任公司 | Method for preparing high-purity lithium ion battery anode material such as lithium manganate |
Non-Patent Citations (1)
| Title |
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| 不同铵盐体系中金属锰在水中的锈蚀速率;唐谟堂等;《中南工业大学学报》;20021231;第33卷(第6期);576-579 * |
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Inventor after: Yang Zhi Inventor after: Ouyang Hongyong Inventor after: Zhang Lifen Inventor after: Xiong Xueliang Inventor before: Yang Zhi Inventor before: Ouyang Hongyong Inventor before: Zhang Lifang Inventor before: Xiong Xueliang |
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