CN100401558C - Method of preparing Li ion cell material-LiNixMn2-X04 - Google Patents

Method of preparing Li ion cell material-LiNixMn2-X04 Download PDF

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CN100401558C
CN100401558C CNB200510055239XA CN200510055239A CN100401558C CN 100401558 C CN100401558 C CN 100401558C CN B200510055239X A CNB200510055239X A CN B200510055239XA CN 200510055239 A CN200510055239 A CN 200510055239A CN 100401558 C CN100401558 C CN 100401558C
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lithium ion
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刘国强
其鲁
晨晖
李卫
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Peking University
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Abstract

The present invention discloses a method for preparing lithium ion battery material LiNi<x>Mn<2-x>O<4>, which comprises the following steps: 1) NH4 HCO3 or (NH4)2CO3 is added in a Mn<2+> solution and a Ni<2+>solution to adjust the pH value to 6 to 9, and basic carbonate solids of Mn and Ni are obtained by reaction; the basic carbonate solids of the Mn and the Ni are decomposed at the temperature of 600 to 650 DEG C. and oxides of the Mn and the Ni are obtained; 3) the obtained oxides of the Mn and the Ni and LiOH H2O or Li2 CO3 are mixed to react under the condition of 750 to 850 DEG C, and the lithium ion battery material LiNi<x>Mn<2-x>O<4> is obtained. The LiNi<x>Mn<2-x>O<4> material obtained and prepared by the method of the present invention is a pure-phase spinel product, Under the charge and discharge scale factor of 0.4C, the primary discharge specific capacity can reach 140 mah/g which approaches to theoretical volume; after charge and discharge are carried out for 50 times, the maximum conservation rate of the volume can be kept more than 90%. The cycle performance of charge and discharge is good, and the present invention has extensive application prospects.

Description

A kind of preparation lithium ion battery material LiNi xMn 2-xO 4Method
Technical field
The present invention relates to lithium ion battery material LiNi xMn 2-xO 4The preparation method.
Background technology
Lithium ion battery is a latest generation secondary accumulator battery after NI-G, Ni-MH battery.Compare with traditional secondary cell, lithium ion battery has outstanding advantage: operating voltage height (3.6V) is NI-G and Ni-MH battery operating voltage three times; Specific energy height (140Wh/kg) is 3 times of nickel-cadmium cell, 1.5 times of Ni-MH battery; Have extended cycle life, lithium ion battery cycle life has reached more than 1000 times at present, can reach several ten thousand times under the low discharge degree of depth; Self discharge little (a month self-discharge rate only is 6-8%) is far below nickel-cadmium cell (25～30%) and Ni-MH battery (30～40%); Memory-less effect can charge at any time as requested, and can not reduce battery performance; Do not have harmful substances in the lithium ion battery, so environmentally safe, be genuine " green battery ".Lithium ion battery has been widely used in the portable electric appts such as mobile phone, notebook computer, miniature camera, and expectation will also can be used widely on ground such as electric automobile, satellite and space flight and space military field.
But a subject matter of lithium ion battery existence at present is that power is still less.The positive electrode that uses in the lithium ion battery mainly contains three kinds now, i.e. LiCoO 2, LiMn 2O 4And LiNiO 2, their operating voltage is all below 4.0V.Want further to improve the performance of lithium ion battery, the essential discharge voltage that improves positive electrode.To material LiMn 2O 4A certain amount of Ni element of middle interpolation can obtain LiNi xMn 2-xO 4(X is 0.2-0.6) material.Behind the Ni element that mixed, the Fermi level E of material FBe improved, thereby improved the operating voltage of battery material.Although structurally, the Ni atom of doping has occupied original LiMn 2O 4The occupied part position of Mn atom in the material, but because material LiNi xMn 2-xO 4Still belong to spinel structure, so material has still kept the stability of spinel.Experimental result shows, through the material LiNi of overdoping xMn 2-xO 4Discharge voltage can reach 4.6V, and have very high discharge capacity and good charge-discharge performance.The discharge voltage of positive electrode improves, can improve the power output of battery, the application of battery will be widened, such as, if be used in the electric motor car, the quantity of so needed series connection and batteries in parallel connection is than with common battery minimizing, for the maintenance and the use of battery brings great convenience, can improve security performance.
At present, synthetic material LiNi xMn 2-xO 4Method mainly comprise sol-gel process (Y.-K.Sun, Y.-S.Lee, M.Yoshio, K.Amine, Electrochem.Solid-State Lett.5 (2002) A99), coprecipitation (T.Ohzuku, S.Takeda, M.Iwanaga, J.Power Sources 81 (1999) 90), latex seasoning (S.-T.Myung, S.Komaba, N.Kumagai, H.Yashiro, H.-T.Chung, T.-H.Cho, Electrochem.Acta 47 (2002) 2543), fused salt synthetic method (J.-H.Kim, S.-T.Myung, Y.-K.Sun, Electrochimica Acta 49 (2004) 219-227) and carbonate precipitation method (Y.S.Lee, Y.K.Sun, S.Ota, T.Miyashita, M.Yoshio, ElectrochemistryCommunications 4 (2002) 989-994) etc., but the discharge capacity first low (between the 125-140mAh/g) of the material that synthesizes with these methods, and its to discharge and recharge stability also poor.Adopt common solid phase synthesis process in addition, with MnO 2, Li 2CO 3And Ni (OH) 2Be raw material synthetic material LiNi under certain conditions xMn 2-xO 4, the angle of diffraction of products therefrom on XRD is 37.5 °, 43.5 ° and 63.4 ° and locates usually to contain NiO and Li xNi 1-xImpurity such as O exist, thereby cause the chemical property of material to reduce.
Summary of the invention
The purpose of this invention is to provide the lithium ion battery material LiNi that a kind of preparation has high power capacity and stable charge-discharge performance xMn 2-xO 4Method.
Preparation lithium ion battery material LiNi provided by the present invention xMn 2-xO 4Method, comprise the steps: 1) to Mn 2+And Ni 2+Add NH in the solution 4HCO 3Or (NH 4) 2CO 3Regulate pH to 6-9, reaction obtains the subcarbonate solid of Mn and Ni; 2) the subcarbonate solid with gained Mn and Ni decomposes down at 600-650 ℃, obtains the oxide of Mn and Ni; 3) with oxide and the LiOHH of gained Mn and Ni 2O or Li 2CO 3Mix, under 750-850 ℃ of condition, react, obtain lithium ion battery material LiNi xMn 2-xO 4Wherein, lithium ion battery material LiNi xMn 2-xO 4In X=0.2-2/3.
Reactive material Mn 2+And Ni 2+With CO 3 2-During reaction, Mn 2+And Ni 2+The mol ratio difference, will obtain the different product of Ni content.Because MnCO 3Solubility product Ksp (MnCO 3) compare NiCO 3Solubility product Ksp (NiCO 3) little, Mn 2+Compare Ni 2+Easily and NH 4HCO 3Reaction generates carbonate deposition, with the described Mn of step 1) 2+And Ni 2+Mn in the solution 2+: Ni 2+Mol ratio be controlled at 2-4: in 1, last getable lithium ion battery material LiNi xMn 2-xO 4Have better electrochemical performance, wherein, Mn 2+: Ni 2+Mol ratio be preferably 2.6: 1, this moment, the gained lithium ion battery material was LiNi 0.5Mn 1.5O 4, the chemical property of this material is best.
The temperature of the described reaction of step 1) is 25-50 ℃, and the reaction mixing speed is 300-600r/min.
Step 2) time of described decomposition reaction generally can be controlled in about 5-10 hour.
Oxide and the LiOHH of described Mn of step 3) and Ni 2The mol ratio of O is 0.22-0.25: 1; Reaction temperature is preferably 780-810 ℃; Reaction time is 5-20 hour, is preferably 8-15 hour.
Synthetic LiNi 0.5Mn 1.5O 4The time course of reaction as follows:
Figure C20051005523900042
Figure C20051005523900043
Figure C20051005523900044
Figure C20051005523900045
The inventive method has following advantage and effect: during owing to synthetic material, before this reactive material was dissolved in the even mixing that has obtained in the solution on molecular level, the subcarbonate chemical stability that contains Mn and Ni that step 1) obtains is good, and Mn and Ni dissolve each other therein, therefore, when carrying out next step reaction, not only reaction temperature is lower, course of reaction just can be finished in air atmosphere, and can also obtain product LiNi free from foreign meter xMn 2-xO 4The LiNi that adopts the inventive method to prepare xMn 2-xO 4Material is the spinelle product of pure phase, and under the 0.4C charge-discharge magnification, the first discharge specific capacity of product can reach 140mAh/g, near theoretical capacity, discharge and recharge 50 times after, the capability retention maximum can remain on more than 90%, charge-discharge performance is fine, has broad application prospects.
Description of drawings
Fig. 1 is LiNi 0.5Mn 1.5O 4Charging and discharging curve;
Fig. 2 is LiNi 0.5Mn 1.5O 4The charge-discharge performance curve;
Fig. 3 is LiNi 0.46Mn 1.54O 4Charging and discharging curve;
Fig. 4 is LiMn 2O 4Charging and discharging curve.
Embodiment
Embodiment 1, LiNi 0.5Mn 1.5O 4Preparation and performance test thereof
The weighing mol ratio is 2.6: 1 Mn (NO 3) 2And Ni (NO 3) 26H 2O is dissolved in them in the aqueous solution, is 30 ℃ in temperature, and mixing speed is to use liquid NH under the condition of 400r/min 4HCO 3Adjusting pH value of solution is 7.2, obtains the subcarbonate solid of manganese and nickel.Under 650 ℃ of high temperature, decomposed 6 hours, make this subcarbonate be decomposed into the oxide of manganese and nickel.With the manganese that obtains and the oxide and the LiOHH of nickel 2O mixed in 0.25: 1 in molar ratio, reacted 15 hours down at 800 ℃, obtained the LiNi of spinel structure 0.5Mn 1.5O 4The granule-morphology of product is spherical in shape, and diameter is 2-5 μ m.
The chemical property of material is tested by the following method: with the LiNi that makes 0.5Mn 1.5O 4(poly-difluoroethylene 5wt%) evenly is coated on the aluminium foil after the mixing, as the positive pole of battery for material and conductive carbon black (5wt%) and PVDF; As negative pole, barrier film is the capillary polypropylene material with metal lithium sheet; Electrolyte is by LiPF 6Be dissolved in ethene carbonic ether (EC) and the propylene carbonate (DMC) formulated, LiPF 6Concentration be 1.0mol/L, the volume ratio of EC and DMC is 1: 1.In being full of the glove box of argon gas, negative electrode, barrier film, electrolyte and anode are assembled into Li/LiPF 6-EC+DMC/LiNi 0.5Mn 1.5O 4Simulated battery has carried out constant current charge-discharge performance test and difference chronopotentiometry with Japanese Bts-2004 detector, and the voltage range of test is 3.5～5.0V, and current density is 0.5mA/cm 2And 2.0mA/cm 2
Material is 0.5mA/cm in current density 2The time charging and discharging curve (with the increase of capacity, what current potential rose is charging curve as shown in Figure 1; With the increase of capacity, what current potential descended is discharge curve), material is 0.5mA/cm in current density 2The time charge-discharge performance curve such as Fig. 2, the result shows, material forms discharge platform at the 4.65V place, discharge capacity is 140mAh/g first, circulates after 50 times, capacity is 134mAh/g, capability retention is 96%.
Material is 2.0mA/cm in current density 2The time and last similar, form discharge platform at the 4.65V place, discharge capacity is 127mAh/g first, circulates after 50 times, capacity is 119mAh/g, capability retention is 94%.
From the charge and discharge process of material as can be seen, material LiNi 0.5Mn 1.5O 4(4.65V) carried out Ni between high voltage region 2+/ Ni 4+Between oxidation and reduction reaction, thereby formed the high voltage charge and discharge platform; And charge and discharge platform does not appear at the 4.0V place, illustrate not have Mn 3+/ Mn 4+Between oxidation and reduction process.
Embodiment 2, LiNi 0.46Mn 1.54O 4Preparation and performance test thereof
The weighing mol ratio is 2.2: 1 Mn (NO 3) 2And Ni (NO 3) 26H 2O is dissolved in them in the aqueous solution, is 30 ℃ in temperature, and mixing speed is to use liquid NH under the condition of 500r/min 4HCO 3Adjusting pH value of solution is 7.4, obtains the subcarbonate solid of manganese and nickel.Under 650 ℃ of high temperature, decompose 8h, make this subcarbonate be decomposed into the oxide of manganese and nickel, then with the manganese that obtains and the oxide and the LiOHH of nickel 2O mixed in 0.24: 1 in molar ratio, carried out 12 hours reaction under 830 ℃, obtained the LiNi of spinel structure 0.46Mn 1.54O 4
Method according to embodiment 1 is measured material LiNi 0.46Mn 1.54O 4Chemical property, be 2.0mA/cm in current density 2Charging and discharging curve as shown in Figure 3, the result shows, material LiNi 0.46Mn 1.54O 4Form discharge platform at the 4.60V place, discharge capacity is 114mAh/g first, and through after 50 charge and discharge cycles, capacity is 91mAh/g, and capability retention is 80%.
LiNi from embodiment 1 and embodiment 2 gained 0.5Mn 1.5O 4And LiNi 0.46Mn 1.54O 4Discharge capacity see that all surpassed the result of bibliographical information, promptly discharge capacity is 95mAh/g (Xianglan Wu, Seung Bin Kim, Journal of Power Sources 109 (2002) 53).
Embodiment 3, LiMn 2O 4Preparation and performance test (Comparative Examples) thereof
With Mn (NO 3) 2Being dissolved in the water, is 30 ℃ in temperature, and mixing speed is to use liquid NH under the condition of 500r/min 4HCO 3Adjusting pH value of solution is 8.0, obtains the carbonate solid of manganese.Under 600 ℃ high temperature, make this carbonate generation decomposition reaction then, then with the oxide and the LiOHH of the manganese that obtains 2O (both mol ratios are 2: 1) carries out 10 hours reaction under 790 ℃, obtain the spinelle product LiMn of pure phase 2O 4
Adopt the chemical property of the method measurement material identical, material LiMn with embodiment 1 2O 4Current density is 0.5mA/cm 2The time charging and discharging curve as shown in Figure 4, the result shows, material LiMn 2O 4At 4.0V and 4.1V place two discharge platforms are arranged, discharge capacity is 120mAh/g first.
Contrast above 3 embodiment, to spinelle LiMn 2O 4Behind the middle doped metallic elements Ni, the dopant material LiNi that obtains xMn 2-xO 4The charging/discharging voltage height, improved the chemical property of material.
Embodiment 4, preparation LiNi 0.38Mn 1.62O 4
The weighing mol ratio is 4: 1 MnSO 4And NiSO 46H 2O is dissolved in them in the aqueous solution, is that 30 ℃, mixing speed are with liquid (NH under the condition of 500r/min in temperature 4) 2CO 3Adjusting pH value of solution is 8.4, obtains the subcarbonate solid of manganese and nickel.Under 600 ℃ of high temperature, decompose 10h, make this subcarbonate be decomposed into the oxide of manganese and nickel, then with the manganese that obtains and the oxide and the Li of nickel 2CO 3Mixed in 0.22: 1 in molar ratio, and under 750 ℃, carried out 18 hours reaction, obtain the LiNi of spinel structure 0.38Mn 1.62O 4
The discharge platform of gained material is 4.63V, and its first charge-discharge capacity is 112mAh/g.

Claims (9)

1. one kind prepares lithium ion battery material LiNi xMn 2-xO 4Method, comprise the steps: 1) to Mn 2+And Ni 2+Add NH in the solution 4HCO 3Or (NH 4) 2CO 3Regulate pH to 6-9, reaction obtains the subcarbonate solid of Mn and Ni; 2) the subcarbonate solid with gained Mn and Ni decomposes down at 600-650 ℃, obtains the oxide of Mn and Ni; 3) with oxide and the LiOHH of gained Mn and Ni 2O or Li 2CO 3Mix, under 750-850 ℃ of condition, react, obtain lithium ion battery material LiNi xMn 2-xO 4Wherein, lithium ion battery material LiNi xMn 2-xO 4In X=0.2-2/3.
2. method according to claim 1 is characterized in that: the described Mn of step 1) 2+And Ni 2+Mn in the solution 2+: Ni 2+Mol ratio be 2-4: 1.
3. method according to claim 2 is characterized in that: the described Mn of step 1) 2+And Ni 2+Mn in the solution 2+: Ni 2+Mol ratio be 2.6: 1.
4. method according to claim 1 is characterized in that: the temperature of the described reaction of step 1) is 25-50 ℃, and the reaction mixing speed is 300-600r/min.
5. method according to claim 1 is characterized in that: step 2) time of described decomposition reaction is 5-10 hour.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: oxide and the LiOHH of described Mn of step 3) and Ni 2O or Li 2CO 3Mol ratio be 0.22-0.25: 1.
7. according to the arbitrary described method of claim 1-5, it is characterized in that: the described reaction temperature of step 3) is 780-810 ℃.
8. method according to claim 7 is characterized in that: the described reaction time of step 3) is 5-20 hour.
9. method according to claim 8 is characterized in that: the described reaction time of step 3) is 8-15 hour.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10308219A (en) * 1997-05-08 1998-11-17 Murata Mfg Co Ltd Manufacture of positive electrode active material for lithium secondary battery
JP2000215884A (en) * 1999-01-25 2000-08-04 Sanyo Electric Co Ltd Positive electrode for nonaqueous electrolyte battery, its manufacture, nonaqueous electrolyte battery using the positive electrode, and manufacture of the battery
CN1585167A (en) * 2003-08-22 2005-02-23 中国科学院成都有机化学有限公司 Lithium ion accumulator positive material and producing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10308219A (en) * 1997-05-08 1998-11-17 Murata Mfg Co Ltd Manufacture of positive electrode active material for lithium secondary battery
JP2000215884A (en) * 1999-01-25 2000-08-04 Sanyo Electric Co Ltd Positive electrode for nonaqueous electrolyte battery, its manufacture, nonaqueous electrolyte battery using the positive electrode, and manufacture of the battery
CN1585167A (en) * 2003-08-22 2005-02-23 中国科学院成都有机化学有限公司 Lithium ion accumulator positive material and producing method thereof

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