CN101859889B - Lithium-manganese composite oxide for active material of anode of secondary lithium battery and preparation method thereof - Google Patents

Lithium-manganese composite oxide for active material of anode of secondary lithium battery and preparation method thereof Download PDF

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CN101859889B
CN101859889B CN2010101882650A CN201010188265A CN101859889B CN 101859889 B CN101859889 B CN 101859889B CN 2010101882650 A CN2010101882650 A CN 2010101882650A CN 201010188265 A CN201010188265 A CN 201010188265A CN 101859889 B CN101859889 B CN 101859889B
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oxide
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mno
lithium
lithium battery
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CN101859889A (en
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杨晓晶
李玉梅
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Beijing Normal University
Beijing Normal University Science Park Technology Development Co Ltd
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Beijing Normal University
Beijing Normal University Science Park Technology Development Co Ltd
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Abstract

The invention provides a lithium-manganese composite oxide for an active material of an anode of a secondary lithium battery, which is characterized in that: the lithium-manganese composite oxide is shown as a general formula (I) Mn-O/M-Mn-O Li4Mn5O12, wherein M is metal; the Mn-O/M-Mn-O is used as a nucleus of the lithium-manganese composite oxide; and the Li4Mn5O12 is clad outside the Mn-O/M-Mn-O to form a shell. Experimental results show that the lithium-manganese composite oxide has high charge and discharge performance when used as the anode material of the lithium battery.

Description

Be used for complex Li-Mn-oxide of active material of anode of secondary lithium battery and preparation method thereof
Technical field
The present invention relates to field of inorganic nonmetallic material, be specifically related to a kind of complex Li-Mn-oxide for lithium battery anode active material and preparation method thereof.
Background technology
Commercialization is succeeded in developing and realized to lithium battery at first by Sony company in nineteen nineties, has been widely used in the portable electric appts, studying it at present and be applied to fields such as electric automobile, hybrid vehicle.As a kind of novel green energy resource battery, lithium battery be hopeful to replace Ni-MH battery and and nickel-cadmium cell, become one of focus of a series of science and technology development plannings in the world about the research work of lithium battery.
One of key factor that influences the lithium battery performance is the activity of anode material of lithium battery, and lithium battery anode active material commonly used at present has LiCoO 2, LiNiO 2, element lithia material such as Ni-Co-Mn, above-mentioned several positive electrodes have higher capacity, for example LiCoO 2The Unit Weight capacity can reach 140-150mAh/g.But above-mentioned different materials also has inevitable defective, as poor heat stability, therefore has serious potential safety hazard; And above-mentioned positive electrode also needs to use expensive and has the Co of toxicity and element such as Ni, therefore uses and is subjected to certain limitation.At present, searching high-energy, stable cycle performance, anode material of lithium battery safe, pollution-free, that cost is low are important research directions of anode material of lithium battery.
Studies show that lithium manganese oxide (LMOs) has Heat stability is good and the high advantage of security performance when being used for lithium battery anode active material; And, because lithium manganese oxide uses aboundresources, with low cost, nontoxic manganese element to replace elements such as Ni and Co, therefore promise to be the most promising anode material of lithium battery.In the prior art, multiple lithium manganese oxide for anode material of lithium battery is disclosed.In known lithium manganese oxygen positive electrode, or battery capacity is low, or circulates steady poor performance, is difficult to satisfy simultaneously the requirement of high power capacity and good cycle.
Consider that there is shortcoming as above in prior art, a kind of complex Li-Mn-oxide for lithium battery anode active material need be provided, this complex Li-Mn-oxide good cycle has higher capacity simultaneously
Summary of the invention
The problem to be solved in the present invention is to provide a kind of complex Li-Mn-oxide for lithium battery anode active material, and this complex Li-Mn-oxide good cycle of this complex Li-Mn-oxide has higher capacity simultaneously.
In order to solve above technical problem, the invention provides a kind of complex Li-Mn-oxide for active material of anode of secondary lithium battery, it is characterized in that described complex Li-Mn-oxide is by formula M n-O/M-Mn-O@Li 4Mn 5O 12(I) expression, in the formula (I), M is metal;
In the complex Li-Mn-oxide shown in the general formula (I), Mn-O/M-Mn-O is as the nuclear of described complex Li-Mn-oxide, Li 4Mn 5O 12The outside that is coated on described Mn-O/M-Mn-O forms shell.
Preferably, Mn-O/M-Mn-O and Li in the described complex Li-Mn-oxide 4Mn 5O 12Mol ratio be 10: 1～1: 10.
Preferably, Mn-O/M-Mn-O and Li in the described complex Li-Mn-oxide 4Mn 5O 12Mol ratio be 5: 1～1: 5.
The present invention is a kind of preparation method of complex Li-Mn-oxide also, it is characterized in that, comprising:
Get the represented manganese oxygen composite particles of formula M n-O/M-Mn-O (II) and mix with lithium salts and obtain mixture, in the formula (II), M is metal;
Heat described mixture to 350 ℃～450 ℃ and make the Li in described Mn-O/M-Mn-O particle surface and the described lithium salts +Li takes place +Insert reaction and generate complex Li-Mn-oxide, described complex Li-Mn-oxide is by formula M n-O/M-Mn-O@Li 4Mn 5O 12(I) expression;
In the complex Li-Mn-oxide shown in the general formula (I), Mn-O/M-Mn-O is as the nuclear of described complex Li-Mn-oxide, Li 4Mn 5O 12The outside that is coated on described Mn-O/M-Mn-O forms shell.
Preferably, described Li +The reaction temperature of inserting reaction is 380 ℃～420 ℃.
Preferably, described Li +The reaction temperature of inserting reaction is 390 ℃～410 ℃.
Preferably, described Li +The reaction time of inserting reaction is 1 hour～20 hours.
Preferably, described lithium salts is one or more in lithium nitrate, lithium chloride, lithium acetate, lithium sulfate or the lithium carbonate.
The present invention also provides a kind of lithium battery anode, comprising:
The described complex Li-Mn-oxide of technique scheme, conductive agent and adhesive.
The present invention also provides a kind of lithium battery, comprising:
The described lithium battery anode of technique scheme; Negative pole; And organic electrolyte solution.
The invention provides the complex Li-Mn-oxide for lithium battery anode active material, it is characterized in that, described complex Li-Mn-oxide is by formula M n-O/M-Mn-O@Li 4Mn 5O 12(I) expression, in the complex Li-Mn-oxide shown in the general formula (I), Mn-O/M-Mn-O is as the nuclear of described complex Li-Mn-oxide, Li 4Mn 5O 12The outside that is coated on described Mn-O/M-Mn-O forms shell.Experimental result shows, this complex Li-Mn-oxide Heat stability is good during as anode material of lithium battery has the favorable charge-discharge performance.
Description of drawings
Fig. 1 is 2000 times SEM figure of the complex Li-Mn-oxide of embodiment 1 preparation;
Fig. 2 is 10,000 times SEM figure of complex Li-Mn-oxide shown in Figure 1;
Fig. 3 is 100,000 times SEM figure of complex Li-Mn-oxide shown in Figure 1;
Fig. 4 is complex Li-Mn-oxide and the α-MnO of embodiment 1 preparation 2X ray diffracting spectrum;
Fig. 5 is preceding 50 the charging and discharging curve figure of lithium battery of embodiment 1 preparation;
Fig. 6 is the charging and discharging lithium battery cycle performance result of embodiment 1 preparation.
Embodiment
In order further to understand the present invention, be described below in conjunction with the preferred embodiment of the invention of embodiment, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The invention provides a kind of complex Li-Mn-oxide, described complex Li-Mn-oxide is by formula M n-O/M-Mn-O@Li 4Mn 5O 12(I) expression, in the complex Li-Mn-oxide shown in the general formula (I), Mn-O/M-Mn-O is as the nuclear of described complex Li-Mn-oxide, Li 4Mn 5O 12The outside that is coated on described Mn-O/M-Mn-O forms shell, and in the general formula (I), M is metal;
According to the present invention, the general formula object lesson can be MnO 2, Mn 2O 3, a kind of in the manganate, be preferably MnO 2, Mn 2O 3Or the manganate of alkali (soil) metal, more preferably MnO 2
According to the present invention, described complex Li-Mn-oxide has nucleocapsid structure, wherein, and as the Li of shell 4Mn 5O 12Be coated on the outside as the Mn-O/M-Mn-O of core, for Mn-O/M-Mn-O and Li in the described lithium manganese oxide 4Mn 5O 12Ratio, there is no particular restriction in the present invention, preferred, Mn-O/M-Mn-O and Li in the described lithium manganese oxide 4Mn 5O 12Be 10: 1～1: 10 according to mol ratio, more preferably 5: 1～1: 5.For the particle diameter of described lithium manganese oxide, the present invention is also without particular limitation, can make the lithium manganese oxide of different-grain diameter as required.
According to the present invention, when preparing the lithium manganese oxide of described nucleocapsid structure, be raw material with the Mn-O/M-Mn-O particle preferably, make described Mn-O/M-Mn-O particle surface and Li then +React and generate Li 4Mn 5O 12Shell, thus the Mn-O/M-Mn-O-Li of nucleocapsid structure obtained 4Mn 5O 12According to the present invention, with Mn-O/M-Mn-O and Li +React and generate Li 4Mn 5O 12Course of reaction called after Li +Insert reaction.The Mn-O/M-Mn-O@Li of nucleocapsid structure provided by the invention 4Mn 5O 12The preparation method specifically comprises:
Get Mn-O/M-Mn-O particle and lithium salts and mix, described lithium salts is preferably the inorganic salts of lithium, and object lesson can be in lithium nitrate, lithium chloride, lithium acetate, lithium sulfate or the lithium carbonate one or more, but is not limited thereto.Preferred lithium salts is lithium nitrate.For the mixed method of Mn-O/M-Mn-O particle and lithium salts, the present invention is also without particular limitation, for example uses machinery or manual stirring method, as long as Mn-O/M-Mn-O particle and lithium salts can be mixed.
After Mn-O/M-Mn-O particle and lithium salts mixed, mixture is placed in the elevated temperature vessel, the preferred elevated temperature container can be the crucible of the ceramic material that do not participate in reacting, and object lesson can be corundum crucible.Cover one deck lithium salts again on the mixture surface then, its objective is protection Li +With the reaction of Mn-O/M-Mn-O, avoid reactant directly to contact with air.For described Li +Inserting the temperature of reaction, is being 350 ℃～430 ℃ preferably, and temperature is crossed when hanging down, and course of reaction is slow, when temperature is too high, generates rock salt phase Li easily 2MnO 3For described Li +Insert the temperature of reaction, more preferably 350 ℃～450 ℃, more preferably 380 ℃～420 ℃, more preferably 390 ℃～410 ℃.For described Li +Insert the reaction time of reaction, be preferably 1 hour～20 hours, the reaction time is the longest not to generate Li with the surface 4Mn 5O 12Other lithium manganese oxide in addition is as the criterion, and the reaction time is the shortest to begin to generate Li with the surface 4Mn 5O 12Be as the criterion, the preferred reaction time is 8 hours～15 hours, housing Li 4Mn 5O 12Thickness can by control Li +Inserting the reaction time controls.
For the source of employed Mn-O/M-Mn-O, there is no particular restriction in the present invention.When Mn-O/M-Mn-O is MnO 2The time, be preferably α-MnO 2(Hollandite), α-MnO 2The preparation method can be method well known to those skilled in the art, for example adopt the normal temperature method synthetic, raw material can be MnSO 4, and (NH 4) 2S 2O 4, two kinds of raw materials are mixed the back under stirring, add the concentrated sulfuric acid, add AgNO then 3React as catalyst, then the reactant that obtains is put in the dark place and leaves standstill, precipitation, filtration, washing obtain α-MnO 2, α-MnO 2Also can buy from the market, to this present invention and without particular limitation.
The present invention also provides a kind of lithium battery anode, comprises the described complex Li-Mn-oxide of technique scheme, conductive agent and adhesive, and conductive agent can be carbon black well known to those skilled in the art, but is not limited thereto.The adhesive object lesson can be vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene or their mixture, but is not limited thereto.When making positive pole, above-mentioned complex Li-Mn-oxide, conductive agent, adhesive can be stirred evenly in solvent, drying makes then, and solvent can be solvents well known to those skilled in the art such as n-formyl sarcolysine base pyrrolidones, acetone, but is not limited thereto.
The present invention also provides a kind of lithium battery, comprises above-mentioned lithium battery anode, negative pole and organic electrolyte solution, and the object lesson of negative pole can be lithium metal, lithium alloy, carbonaceous material and graphite, but is not limited thereto.Organic electrolyte solution can be for being dissolved with the electrolyte solvent of lithium salts, and the lithium salts object lesson can be LiClO 4, LiCF 3SO 3, LiPF 6, LiN (CF 3SO 2), LiBF 4, LiC (CF 3SO 2) 3Or LiN (C 2F 5SO 2) 2, electrolyte solvent can be a kind of in ethylene carbonate well known to those skilled in the art, diethyl carbonate, the dimethyl carbonate or their mixture, the concentration of lithium salts can be 0.5M～2M in the organic electrolyte solution.According to the present invention, can also between positive pole and negative pole, barrier film be set, the object lesson of barrier film can be glass fibre, polyester, polyethylene, polypropylene, polytetrafluoroethylene or their mixture, there is no particular restriction to this present invention.
Embodiment 1
Preparation α-MnO 2Particle:
In 200ml water, add the MnSO of 8mmol respectively 4(NH 4) 2SO 4, under stirring, add the 8ml concentrated sulfuric acid successively and add an amount of AgNO 3As catalyst, stop to stir behind the reaction 10min, reactant is put in the dark place left standstill 2 days, precipitation is filtered sediment, and water and absolute ethanol washing obtain α-MnO at 70 ℃ with drying precipitate then successively 2Particle.
Get the described α-MnO of 0.2g 2With 2.0g LiNO 3In agate mortar, pack into behind the mixing in the corundum crucible, get an amount of LiNO again 3Cover the MnO in the described crucible 2With 2.0g LiNO 3The mixture surface; Heating crucible to 400 ℃ reacts, and the reaction time is 12h, and the product water that obtains and absolute ethanol washing, filtration obtain complex Li-Mn-oxide MnO in 70 ℃ of dryings then 2-Li 4Mn 5O 12, get the complex Li-Mn-oxide that makes and carry out SEM observation, x-ray diffraction experiment, charge-discharge performance experiment successively.
(1), SEM observed result
Get the complex Li-Mn-oxide that makes and carry out the SEM observation, result such as Fig. 1, Fig. 2, Fig. 3, Fig. 1 are 200 times SEM figure, and Fig. 2 is 10,000 times SEM figure, and Fig. 3 is 100,000 SEM figure, can be clearly seen that the lithium manganese oxide MnO that obtains from figure 2-Li 4Mn 5O 12Be that particle diameter is the micron ball of 4-6 μ m, the housing diameter of ball is about 20-30nm, has nucleocapsid structure.
(2) X-ray diffraction result
Get α-MnO respectively 2With the complex Li-Mn-oxide MnO that makes 2-Li 4Mn 5O 12Carry out X-ray diffraction, the results are shown in Figure curve a and curve b in 4, wherein curve a is α-MnO 2Diffracting spectrum, curve b are MnO 2-Li 4Mn 5O 12X ray diffracting spectrum.
In curve b, clearly marked α-MnO 2Diffraction maximum and Li 4Mn 5O 13Diffraction maximum, namely with inverted triangle
Figure GSA00000140776800061
α-the MnO of expression 2Diffraction maximum, other peak are spinelle phase Li with standard JCPDS card 46-0810 then 4Mn 5O 12Corresponding, instruction card has been looked unfamiliar into spinelle phase Li 4Mn 5O 12
(3) discharge and recharge experiment
The 70 weight portion complex Li-Mn-oxides of getting present embodiment preparation evenly mix as the acetylene black (KS-6) of conductive agent with 20 weight portions as positive electrode active materials, add the polyvinylidene fluoride binder solution then and mix and spread upon that drying obtains cathode film on the aluminium foil that thickness is 15 μ m.Adopt the lithium sheet as negative plate, adopt the UBE film of Ube company production as barrier film, use to comprise that concentration is 1.0M LiPF 6Ethylene carbonate (EC): diethyl carbonate (DEC): as electrolyte solution, voltage-operated scope was 2.0-4.0V to dimethyl carbonate (DMCA) according to 1: 1: 1 mixed solvent, and current density is 10mA/g.The electric performance test result as shown in Figure 5 and Figure 6.Wherein, Fig. 5 is preceding 50 times charging and discharging curve, and Fig. 6 is cycle performance.As shown in Figure 5, in that a charging and discharge platform are arranged respectively about 3.0v and about 2.8v, shown Li 4Mn 5O 12The characteristics that discharge and recharge; As can be seen from Figure 6, the charge/discharge capacity of battery is along with the increase of cycle-index presents the trend of increase, good cycle.
More than to the Mn-O/M-Mn-O@Li of nucleocapsid structure provided by the present invention 4Mn 5O 12And preparation method thereof be described in detail.Used specific case herein principle of the present invention and execution mode are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.

Claims (4)

1. a complex Li-Mn-oxide that is used for active material of anode of secondary lithium battery is characterized in that described complex Li-Mn-oxide is by formula M nO 2@Li 4Mn 5O 12(I) expression;
In the complex Li-Mn-oxide shown in the general formula (I), MnO 2As the nuclear of described complex Li-Mn-oxide, Li 4Mn 5O 12Be coated on described MnO 2The outside form shell;
The preparation method of described complex Li-Mn-oxide is for being specially:
In 200ml water, add the MnSO of 8mmol respectively 4(NH 4) 2SO 4, under stirring, add the 8ml concentrated sulfuric acid successively and add an amount of AgNO 3As catalyst, stop to stir behind the reaction 10min, reactant is put in the dark place left standstill 2 days, precipitation is filtered sediment, and water and absolute ethanol washing obtain α-MnO at 70 ℃ with drying precipitate then successively 2Particle;
Get the described α-MnO of 0.2g 2With 2.0g LiNO 3In agate mortar, pack into behind the mixing in the corundum crucible, get an amount of LiNO again 3Cover the MnO in the described crucible 2With 2.0g LiNO 3The mixture surface; Heating crucible to 400 ℃ reacts, and the reaction time is 12h, and the product water that obtains and absolute ethanol washing, filtration obtain complex Li-Mn-oxide in 70 ℃ of dryings then.
2. the preparation method of a complex Li-Mn-oxide is characterized in that, comprising:
In 200ml water, add the MnSO of 8mmol respectively 4(NH 4) 2SO 4, under stirring, add the 8ml concentrated sulfuric acid successively and add an amount of AgNO 3As catalyst, stop to stir behind the reaction 10min, reactant is put in the dark place left standstill 2 days, precipitation is filtered sediment, and water and absolute ethanol washing obtain α-MnO at 70 ℃ with drying precipitate then successively 2Particle;
Get the described α-MnO of 0.2g 2With 2.0g LiNO 3In agate mortar, pack into behind the mixing in the corundum crucible, get an amount of LiNO again 3Cover the MnO in the described crucible 2With 2.0g LiNO 3The mixture surface; Heating crucible to 400 ℃ reacts, and the reaction time is 12h, and the product water that obtains and absolute ethanol washing, filtration obtain complex Li-Mn-oxide in 70 ℃ of dryings then; Described complex Li-Mn-oxide is by formula M nO 2@Li 4Mn 5O 12(I) expression;
In the complex Li-Mn-oxide shown in the general formula (I), MnO 2As the nuclear of described complex Li-Mn-oxide, Li 4Mn 5O 12Be coated on described MnO 2The outside form shell.
3. lithium battery anode comprises:
The described complex Li-Mn-oxide of claim 1, conductive agent and adhesive.
4. lithium battery comprises:
The described lithium battery anode of claim 3;
Negative pole; And organic electrolyte solution.
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US5240794A (en) * 1990-12-20 1993-08-31 Technology Finance Corporation (Proprietary) Limited Electrochemical cell

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US5240794A (en) * 1990-12-20 1993-08-31 Technology Finance Corporation (Proprietary) Limited Electrochemical cell

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Xiaojing Yang et al..Synthesis of Li1.33Mn1.67O4 spinels with different morphologies and their ion adsorptivities after delithiation.《Journal of materials chemistry》.2000,第10卷1903-1909.

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