CN107591531A - A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application - Google Patents
A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application.The preparation method comprises the following steps：(1) it is transition metal salt is scattered in a solvent, obtain metal salt solution；(2) it is lithium salts and sodium salt is scattered in a solvent, obtain mixed solution I；(3) metal salt solution obtained in step (1) is added in oxalic acid solution and reacted, obtain reaction solution II；(4) mixed solution I obtained in step (2) is distributed in the reaction solution II obtained in step (3), be then freeze-dried, then pulverized, obtain precursor powder；(5) precursor powder obtained in step (4) is calcined, obtains lithium/sodium double ion manganese-base oxide positive electrode.Lithium ion battery and the common advantage of sodium-ion battery are played in the present invention, realizes that double ion acts synergistically, product well-crystallized, shows good chemical property, higher specific capacity and good cyclical stability.
Description
Technical field
The invention belongs to novel energy field of material technology, more particularly to a kind of lithium/sodium double ion manganese-base oxide positive pole
Material and preparation method and application.
Background technology
Due to high-energy-density, the advantages of high stored energy capacitance and long circulation life, rechargeable lithium ion batteries cause people
Extensive concern.Nowadays, rechargeable lithium ion batteries are applied in many electronic equipments, including smart mobile phone, pen
Remember this computer and electric automobile.It is well known that for the angle of cost and energy density, positive electrode is in lithium ion battery
Play important role.In lithium ion battery, cobalt acid lithium is commercialization positive electrode that is earliest and being widely used, because
Its synthetic method is simple, possesses good reversible charge-discharge performance and stable discharge platform.But due to the reality of cobalt acid lithium
Specific capacity is relatively low (for 140mAh g-1), safety problem be present and the limitation for the factors such as cost is higher, excite researcher and probe into
Other cheap, more feasible positive electrodes are used as the substitute of cobalt acid lithium.
In recent years, stratiform ternary nickel, cobalt and manganese oxide anode material, the excellent of lithium nickelate, cobalt acid lithium and LiMn2O4 is incorporated
Gesture, reduce expensive in positive electrode and virose cobalt dosage.In addition, ternary material has good tolerance to high voltage
Property, there is height ratio capacity, higher energy density is most hopeful to substitute cobalt acid lithium in electronic product, and is in electrokinetic cell
In mixed with LiMn2O4 application novel anode material, therefore, the ternary nickel cobalt manganese material LiNi of compound systemxCoyMn1-x-yO2
(NCM) focus of research is turned into.And manganese-base oxide positive electrode can not only reduce cost of material, safety can also be improved
Property and stability, it is considered to be promising, commercially viable positive electrode of future generation.In actual applications, can be to ternary
Material, which is doped, to be modified to improve its chemical property.For example, after lithium doping, the reversible capacity and cycle performance of material obtain
Raising is arrived；The doping of fluorine, initial capacity can decline, but cycle performance and security performance significantly improve；Magnesium and fluorine
Co-doped, capacity, cycle performance are significantly improved, and hot property has clear improvement.
Although lithium/sodium double ion manganese-base oxide positive electrode has many advantages, such as, in actual application there is also
Some shortcomings, such as efficiency is low first, discharge platform (3.7V vs.Li+/ Li or so) relative cobalt acid lithium (3.9V) is relatively low, and lithium
The mixing of layer cationic, first charge-discharge efficiency and cyclical stability to material all have an impact.
The content of the invention
The shortcomings that primary and foremost purpose of the present invention is to overcome prior art and deficiency, there is provided a kind of lithium/sodium double ion manganese base
The preparation method of oxide anode material.
Lithium/sodium double ion manganese-base oxide positive pole the material being prepared another object of the present invention is to provide methods described
Material.
A further object of the present invention is the application for providing the lithium/sodium double ion manganese-base oxide positive electrode.
It is still another object of the present invention to provide the half-cell containing lithium/sodium double ion manganese-base oxide positive electrode.
The purpose of the present invention is achieved through the following technical solutions：A kind of lithium/sodium double ion manganese-base oxide positive electrode
Preparation method, comprise the following steps：
(1) it is transition metal salt is scattered in a solvent, obtain metal salt solution；
(2) it is lithium salts and sodium salt is scattered in a solvent, obtain mixed solution I；
(3) metal salt solution obtained in step (1) is added in oxalic acid solution and reacted, obtain reaction solution
II；
(4) mixed solution I obtained in step (2) is distributed in the reaction solution II obtained in step (3), Ran Houleng
It is lyophilized dry, then pulverize, obtain precursor powder；
(5) precursor powder obtained in step (4) is calcined, obtains lithium/sodium double ion manganese-base oxide positive electrode.
The metallic element in transition metal salt described in step (1) is manganese element, nickel element and cobalt element；Three kinds of elements
Content can be arbitrary proportion.
Transition metal salt described in step (1) is at least one of acetate, sulfate, nitrate and chlorate；
Preferably manganese acetate, nickel acetate and cobalt acetate；More preferably four hydration manganese acetates, four hydration nickel acetates and four hydration cobalt acetates；
Most preferably four hydration manganese acetates, four hydration nickel acetates and four hydration cobalt acetates in molar ratio 0.534：0.133：0.133 proportioning
The transition metal salt being mixed to get.
The concentration of metal salt solution described in step (1) is preferably 0.5~2.0mol/L.
The preferred deionized water of solvent described in step (1) and (2).
Lithium salts described in step (2) is at least one of lithium acetate, lithium sulfate, lithium nitrate and lithium chloride；Preferably
The lithium salts (uniformity that ensures acid ion) consistent with the acid ion in the metal salt solution；More preferably lithium acetate.
Sodium salt described in step (2) is at least one of sodium acetate, sodium sulphate, sodium nitrate and sodium chloride；Preferably
The sodium salt (uniformity that ensures acid ion) consistent with the acid ion in the metal salt solution；More preferably sodium acetate.
The mol ratio of the sodium element in the elemental lithium and sodium salt in lithium salts described in step (2) is 0.7~1.1：0.1~
0.5, while need to meet that the mol ratio numerical value of elemental lithium and sodium element is added up as 1.2.
Oxalic acid solution described in step (3) is scattered in the solution obtained in solvent for oxalic acid.
The preferred deionized water of described solvent.
The concentration of oxalic acid solution described in step (3) is preferably 0.1~2.0mol/L.
The content of the oxalate denominationby in oxalic acid solution described in step (3) is no less than metal in transition metal salt solution
The content of ion, it is therefore an objective to which metal ion is precipitated into (MC completely2O4)；Oxalate denominationby and transition metal salt in oxalic acid solution
The mol ratio of metal ion in solution is preferably 1~1.05：1；Preferably 1.03：1.
Reaction described in step (3) is preferably stirring reaction；Make its anti-by the way of more preferably being stirred while being added dropwise
Should be abundant, continue 2~5h of stirring after dripping.
The speed of described stirring is 600~1000rpm.
The speed of described dropwise addition is preferably 1~2d/s.
Described in step (4) it is scattered be preferably using stir by the way of disperseed；Preferably use and stirred when being added dropwise
The mode mixed is disperseed；More preferably being stirred when being added dropwise makes it well mixed, continues 0.5~5h of stirring after dripping.
The speed of described stirring is 600~1000rpm.
The speed of described dropwise addition is preferably 1~2d/s.
Transition metal in lithium, the summation of sodium element and precursor powder in precursor powder described in step (4)
Mol ratio be preferably 1.0~1.5：1.
The condition of freeze-drying described in step (4) is preferably：Less than -40 DEG C freezing 10h, are subsequently placed in 20Pa vacuum
In condition, moisture therein is directly sublimed into gaseous state without liquid, finally dry material dewatering, evaporate reaction system
Solvent is without losing lithium and sodium.
The condition of calcining described in step (5) is：450~600 DEG C calcining 4~6h, then 700~950 DEG C calcining 5~
24h；The condition of calcining is preferably：In air atmosphere, 500 DEG C of calcining 5h, then 12h is calcined for 900 DEG C.
A kind of lithium/sodium double ion manganese-base oxide positive electrode, is prepared by the method described in any of the above-described.
Described lithium/application of the sodium double ion manganese-base oxide positive electrode in field of lithium ion battery.
A kind of half-cell containing lithium/sodium double ion manganese-base oxide positive electrode, its assemble method comprise the following steps：
(I) above-mentioned lithium/sodium double ion manganese-base oxide positive electrode, binding agent and conductive agent is well mixed, Ran Houyong
Solvent is tuned into slurry, coated on aluminium foil, then be dried in vacuo, roll-in, section, obtain positive plate；
(II) positive plate that will be obtained in step (1), electrolyte barrier film and are assembled to electrode, obtained containing lithium/sodium
The half-cell of double ion manganese-base oxide positive electrode.
Binding agent described in step (I) is preferably binding agent PVDF.
Conductive agent described in step (I) is preferably conductive agent Super-P.
The mass ratio of lithium/sodium double ion manganese-base oxide positive electrode, binding agent and conductive agent described in step (I) is excellent
Elect 8 as:1:1.
Solvent described in step (I) is preferably 1-METHYLPYRROLIDONE.
Aluminium foil described in step (I) is preferably 10 μm of aluminium foil.
Positive plate described in step (I) is preferably diameter 18mm positive plate.
Electrolyte described in step (II) is preferably Li+/Na+Double ion mixed electrolytic solution.
Described Li+/Na+Double ion mixed electrolytic solution is made up of solute and mixed solvent；Wherein, described solute is
LiPF6Solution and NaPF6Solution, described mixed solvent are EC (ethylene carbonate), DMC (dimethyl carbonate) and EMC (carbonic acid
Methyl ethyl ester).
Described LiPF6Solution and NaPF6The volume ratio of solution is 1~11：1；Preferably 3：1.
Described LiPF6The concentration of solution is preferably 1mol/L.
Described NaPF6The concentration of solution is preferably 1mol/L.
Described EC (ethylene carbonate), DMC (dimethyl carbonate) and EMC (methyl ethyl carbonate) volume ratio are preferably 1：
1：1.
Barrier film described in step (II) is preferably microporous polypropylene membrane Celgard-2400.
Described in step (II) is preferably metal lithium sheet to electrode.
The assembling of the described half-cell containing lithium/sodium double ion manganese-base oxide positive electrode is preferably in protectiveness gas
Assembled under atmosphere.
The principle of the present invention：
By the acetate of the oxalic acid of metered proportions, nickel and cobalt and manganese mix, generation precipitation (coprecipitation), be blended into lithium and
The acetate of sodium, presoma is obtained, is handled at high temperature, obtain lithium/sodium double ion manganese-base oxide positive electrode.The manganese base of natrium doping
Oxide anode material, due to ionic radius Na+(0.102nm) compares Li+(0.076nm) greatly, introduces Na and extends Li+It is mobile logical
Road and the spacing for expanding Li interlayers, while coordinate Li+/Na+Mixed electrolytic solution is assembling lithium/sodium double ion manganese-base oxide just
Pole material.During charging, the effect of lithium ion and sodium ion in lithium/sodium double ion manganese-base oxide positive electrode in external electric field
Under, by Li+/Na+Mixed electrolytic solution migrates to negative pole, embedded negative pole；During electric discharge, lithium ion and sodium ion insertion positive pole.It is mixed into
Na+Electrolyte improve the diffusion rate of lithium ion and sodium ion to cooperate with, improve its cycle performance so as to reach, improving it can
The purpose of inverse capacity.
The present invention is had the following advantages relative to prior art and effect：
1st, the invention provides double ion Li+/Na+Electrolyte coordinates the preparation of the manganese-base oxide positive electrode of natrium doping
Theory and method, this method technique is simple and convenient to operate, cost is cheap, green, product well-crystallized, is shown good
Chemical property, can be good at improve battery specific discharge capacity and cyclical stability.
2nd, presoma is prepared using coprecipitation in the present invention, and the manganese base that natrium doping is then obtained through high temperature sintering aoxidizes
Thing positive electrode, the grain diameter of material is smaller (1~2 μm), good crystallinity, and coordinates Li+/Na+Mixed electrolytic solution, lithium/sodium are double
Ion manganese-base oxide positive electrode electrochemical performance, stable cycle performance, specific capacity improve.
3rd, compared with traditional lithium ion battery, traditional lithium ion battery only has one in charge/discharge process is carried out
Kind ion (i.e. lithium ion) is transported as medium between the both positive and negative polarity of inside battery, and the present invention is to be based on lithium ion battery
The common advantageous feature with sodium-ion battery, transporting for two kinds of ions of lithium ion/sodium ion is realized inside a kind of battery system,
And positive electrode is to provide the source of inside battery ion transport.
4th, the positive electrode that synthesizes contains two kinds of elements of lithium/sodium in the present invention, and provide for lithium/sodium double ion it is compound
Electrolyte, have in charge/discharge process two kinds of ions (i.e. lithium ion/sodium ion) as medium inside battery both positive and negative polarity
Between transported.So as to realize that double ion acts synergistically, lithium ion battery and the common advantage of sodium-ion battery are played, and is carried
The positive electrode of confession is lithium/sodium double ion manganese-base oxide as positive electrode active materials.
Brief description of the drawings
Fig. 1 is the XRD spectrogram of lithium made from embodiment 1~3/sodium double ion manganese-base oxide positive electrode.
Fig. 2 is the SEM spectrum figure of presoma made from embodiment 1.
Fig. 3 is the SEM spectrum figure of lithium made from embodiment 1/sodium double ion manganese-base oxide positive electrode.
Fig. 4 is the charge-discharge performance figure of lithium made from embodiment 1/sodium double ion manganese-base oxide positive electrode.
Fig. 5 is made from the preparation technology flow chart and embodiment 2 of invention lithium/sodium double ion manganese-base oxide positive electrode
The charge-discharge performance figure of lithium/sodium double ion manganese-base oxide positive electrode；Wherein, it is process chart to scheme A, and figure B is to fill
Discharge cycle performance figure.
Fig. 6 is the charge-discharge performance figure of lithium made from embodiment 3/sodium double ion manganese-base oxide positive electrode.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
In following case study on implementation, obtained lithium/sodium double ion manganese-base oxide is as positive electrode active materials, with binding agent
PVDF, conductive agent Super-P are according to 8:1:1 mass ratio mixing, is tuned into slurry by solvent of 1-METHYLPYRROLIDONE, is coated in
On 10 μm of aluminium foil, and vacuum dried, roll-in, section, diameter 18mm positive plate is made, electrolyte is 1mol/L by solute
LiPF6：1mol/L NaPF6=0.9:0.3, v/v, at mixed solvent EC (ethylene carbonate)：DMC (dimethyl carbonate)：EMC
(methyl ethyl carbonate)=1：1：It is formulated in 1, v/v/v solution, barrier film is microporous polypropylene membrane Celgard-2400, to electrode
For metal lithium sheet, CR2430 type half-cells are assembled into the glove box full of argon gas.Under normal temperature condition, using Wuhan gold promise electricity
The chemical property of sub- Co., Ltd LAND battery test systems test battery, in 25mA g-1Current density under carry out permanent electricity
Charge-discharge test is flowed, charging/discharging voltage scope control is in 2.0V~4.65V.
Embodiment 1
(1) 4.09g tetra- is hydrated manganese acetate, 1.04g tetra- is hydrated nickel acetate and 1.04g tetra- is hydrated cobalt acetate and is dispersed in 25mL
In deionized water, hybrid transition metal salting liquid is obtained；
(2) oxalic acid hydrates of 5.7g bis- are dispersed in 100mL deionized waters, obtain oxalic acid solution；
(3) 2.385g anhydrous lithium acetates and 0.269g anhydrous sodium acetates are dispersed in 25mL deionized waters.Wherein, lithium salts
The lithium that excessive 5%wt is volatilized with supplementing in calcination process；
(4) the hybrid transition metal salting liquid in step (1) is added in the oxalic acid solution of step (2), when being added dropwise
Stirring makes its reaction abundant, mixing speed 800rmp, continues to stir 2h after dripping, stirring makes reaction system mixing scattered equal
It is even, be advantageous to the abundant progress of reaction；
(5) lithium acetate for preparing step (3), sodium acetate solution are added in the solution of step (4) reaction, when being added dropwise
Stirring makes it well mixed, mixing speed 800rmp, continues to stir 0.5h after dripping, be then freeze-dried solution (-
Less than 40 DEG C freezing 10h, then make moisture therein be directly sublimed into gaseous state without liquid, finally make material under the pa of vacuum 20
Dehydrate), the solvent of reaction system is evaporated without losing lithium, sodium, then grinds to obtain precursor powder；
(6) precursor powder made from step (5) is calcined in air atmosphere, 500 DEG C of calcining 5h, then forged for 900 DEG C
12h is burnt, obtains lithium/sodium double ion manganese-base oxide positive electrode (NCM-0.1).
Positive electrode sample made from this example is subjected to X-ray diffraction analysis, as a result as shown in figure 1, can from Fig. 1
Go out, sample made from this example has α-NaFeO2Type layer structure (space group R-3m), main diffraction maximum at 18.6 °,
Near 37.0 ° and 44.7 °.It is Li positioned at 20~25 ° of diffraction maximums2MnO3(C2/m) characteristic peak.In addition, in (006)/(012)
(018)/(110) have obvious division peak at two, illustrate obtained by sample have preferable layer structure.And there is no other in figure
The diffraction maximum of impurity, show that the material without other phases produces, product purity is high.Fig. 2 is the SEM of presoma made from step (5)
Figure, it can be seen that foring spherical morphology by coprecipitation reaction.Fig. 3 be lithium sodium made from this embodiment it is double from
The SEM figures of sub- manganese-base oxide positive electrode, it can be seen that material morphology is substantially unchanged after high temperature sintering twice,
The second particle particle diameter formed is accumulated at 1~2 μm.Fig. 4 is the charge-discharge performance of positive electrode made from this embodiment 1
Figure, as shown in Figure 4, initial charge specific capacity is 287.6mAh g-1, cycle efficieny is 72.5% first.Circulation 20 weeks, specific capacity
Also it is maintained at 229.9mAh g-1More than, cycle performance is excellent.
Embodiment 2
(1) 4.09g tetra- is hydrated manganese acetate, 1.04g tetra- is hydrated nickel acetate and 1.04g tetra- is hydrated cobalt acetate and is dispersed in 25mL
In deionized water, hybrid transition metal salting liquid is obtained；
(2) oxalic acid hydrates of 5.7g bis- are dispersed in 100mL deionized waters, obtain oxalic acid solution；
(3) 1.95g anhydrous lithium acetates and 0.808g anhydrous sodium acetates are dispersed in 25mL deionized waters.Wherein, lithium salts
The lithium that excessive 5%wt is volatilized with supplementing in calcination process；
(4) the hybrid transition metal salting liquid in step (1) is added in the oxalic acid solution of step (2), when being added dropwise
Stirring makes its reaction abundant, mixing speed 800rmp, continues to stir 2h after dripping；
(5) lithium acetate for preparing step (3), sodium acetate solution are added in the solution of step (4) reaction, when being added dropwise
Stirring makes it well mixed, mixing speed 800rmp, continues to stir 0.5h after dripping, be then freeze-dried solution (-
Less than 40 DEG C freezing 10h, then make moisture therein be directly sublimed into gaseous state without liquid, finally make material under the pa of vacuum 20
Dehydrate), the solvent of reaction system is evaporated without losing lithium, sodium, then grinds to obtain precursor powder；
(6) precursor powder made from step (5) is calcined in air atmosphere, 500 DEG C of calcining 5h, then forged for 900 DEG C
12h is burnt, obtains lithium/sodium double ion manganese-base oxide positive electrode (NCM-0.3)；
Positive electrode sample made from this example is subjected to X-ray diffraction analysis, as a result as shown in figure 1, can from Fig. 1
Go out, sample made from this example has α-NaFeO2Type layer structure (space group R-3m), main diffraction maximum at 18.6 °,
Near 37.0 ° and 44.7 °.It is Li positioned at 20~25 ° of diffraction maximums2MnO3(C2/m) characteristic peak.In addition, in (006)/(012)
(018)/(110) have obvious division peak at two, illustrate obtained by sample have preferable layer structure.And there is no other in figure
The diffraction maximum of impurity, show that the material without other phases produces, product purity is high.Fig. 5 is positive electrode made from this embodiment 1
Charge-discharge performance figure, as shown in Figure 5, initial charge specific capacity is 274.6mAh g-1, first cycle efficieny be
76.3%.Circulation 20 weeks, specific capacity is also maintained at 249.2mAh g-1More than, cycle performance is excellent.
Embodiment 3
(1) 4.09g tetra- is hydrated manganese acetate, 1.04g tetra- is hydrated nickel acetate and 1.04g tetra- is hydrated cobalt acetate and is dispersed in 25mL
In deionized water, hybrid transition metal salting liquid is obtained；
(2) oxalic acid hydrates of 5.7g bis- are dispersed in 100mL deionized waters, obtain oxalic acid solution；
(3) 1.517g anhydrous lithium acetates and 1.346g anhydrous sodium acetates are dispersed in 25mL deionized waters.Wherein, lithium salts
The lithium that excessive 5%wt is volatilized with supplementing in calcination process；
(4) the hybrid transition metal salting liquid in step (1) is added in the oxalic acid solution of step (2), when being added dropwise
Stirring makes its reaction abundant, mixing speed 800rmp, continues to stir 2h after dripping；
(5) lithium acetate for preparing step (3), sodium acetate solution are added in the solution of step (4) reaction, when being added dropwise
Stirring makes it well mixed, mixing speed 800rmp, continues to stir 0.5h after dripping, be then freeze-dried solution (-
Less than 40 DEG C freezing 10h, then make moisture therein be directly sublimed into gaseous state without liquid, finally make material under the pa of vacuum 20
Dehydrate), the solvent of reaction system is evaporated without losing lithium, sodium, then grinds to obtain precursor powder；
(6) precursor powder made from step (5) is calcined in air atmosphere, 500 DEG C of calcining 5h, then forged for 900 DEG C
12h is burnt, obtains lithium/sodium double ion manganese-base oxide positive electrode (NCM-0.5)；
Positive electrode sample made from this example is subjected to X-ray diffraction analysis, as a result as shown in figure 1, can from Fig. 1
Go out, sample made from this example has α-NaFeO2Type layer structure (space group R-3m), main diffraction maximum at 18.6 °,
Near 37.0 ° and 44.7 °.It is Li positioned at 20~25 ° of diffraction maximums2MnO3(C2/m) characteristic peak.In addition, in (006)/(012)
(018)/(110) have obvious division peak at two, illustrate obtained by sample have preferable layer structure.And there is no other in figure
The diffraction maximum of impurity, show that the material without other phases produces, product purity is high.Fig. 6 is positive electrode made from this embodiment 3
Charge-discharge performance figure, it will be appreciated from fig. 6 that initial charge specific capacity is 255.1mAh g-1, first cycle efficieny be
79.3%.Circulation 20 weeks, specific capacity is also maintained at 216.4mAh g-1More than, cycle performance is excellent.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of lithium/sodium double ion manganese-base oxide positive electrode, it is characterised in that comprise the following steps：
(1) it is transition metal salt is scattered in a solvent, obtain metal salt solution；
(2) it is lithium salts and sodium salt is scattered in a solvent, obtain mixed solution I；
(3) metal salt solution obtained in step (1) is added in oxalic acid solution and reacted, obtain reaction solution II；
(4) mixed solution I obtained in step (2) is distributed in the reaction solution II obtained in step (3), then freezing is dry
It is dry, then pulverize, obtain precursor powder；
(5) precursor powder obtained in step (4) is calcined, obtains lithium/sodium double ion manganese-base oxide positive electrode.
2. the preparation method of lithium according to claim 1/sodium double ion manganese-base oxide positive electrode, it is characterised in that：
The metallic element in transition metal salt described in step (1) is manganese element, nickel element and cobalt element；
The mol ratio of the sodium element in the elemental lithium and sodium salt in lithium salts described in step (2) is 0.7~1.1：0.1~0.5.
3. the preparation method of lithium according to claim 1/sodium double ion manganese-base oxide positive electrode, it is characterised in that：
Transition metal salt described in step (1) is at least one of acetate, sulfate, nitrate and chlorate；
Lithium salts described in step (2) is at least one of lithium acetate, lithium sulfate, lithium nitrate and lithium chloride；
Sodium salt described in step (2) is at least one of sodium acetate, sodium sulphate, sodium nitrate and sodium chloride.
4. the preparation method of lithium according to claim 1/sodium double ion manganese-base oxide positive electrode, it is characterised in that：
The concentration of metal salt solution described in step (1) is 0.5~2.0mol/L；
The concentration of oxalic acid solution described in step (3) is 0.1~2.0mol/L；
The mol ratio of the metal ion in the oxalate denominationby and transition metal salt solution in oxalic acid solution described in step (3)
For 1~1.05：1；
Transition metal rubs in lithium, the summation of sodium element and precursor powder in precursor powder described in step (4)
That ratio preferably 1.0~1.5：1.
5. the preparation method of lithium according to claim 1/sodium double ion manganese-base oxide positive electrode, it is characterised in that：
Transition metal salt described in step (1) is manganese acetate, nickel acetate and cobalt acetate；
Solvent deionized water described in step (1) and (2)；
Reaction described in step (3) is stirring reaction, and the speed of stirring is 600~1000rpm；
Being separated into described in step (4) is disperseed by the way of stirring, and the speed of stirring is 600~1000rpm；
The condition of freeze-drying described in step (4) is：Less than -40 DEG C freezing 10h, are subsequently placed in 20Pa vacuum conditions
Row drying；
The condition of calcining described in step (5) is：450~600 DEG C of 4~6h of calcining, then calcine 5~24h for 700~950 DEG C.
A kind of 6. lithium/sodium double ion manganese-base oxide positive electrode, it is characterised in that：By described in any one of Claims 1 to 5
Method be prepared.
7. lithium/application of the sodium double ion manganese-base oxide positive electrode in field of lithium ion battery described in claim 6.
8. a kind of half-cell containing lithium/sodium double ion manganese-base oxide positive electrode, it is characterised in that its assemble method includes
Following steps：
(I) lithium described in claim 6/sodium double ion manganese-base oxide positive electrode, binding agent and conductive agent is well mixed,
Then be tuned into slurry with solvent, coated on aluminium foil, then be dried in vacuo, roll-in, section, obtain positive plate；
(II) positive plate that will be obtained in step (1), electrolyte and assemble barrier film to electrode, obtain containing lithium/sodium it is double from
The half-cell of sub- manganese-base oxide positive electrode.
9. the half-cell according to claim 8 containing lithium/sodium double ion manganese-base oxide positive electrode, its feature exist
In：
Electrolyte described in step (II) is Li+/Na+Double ion mixed electrolytic solution；
Described Li+/Na+Double ion mixed electrolytic solution is made up of solute and mixed solvent；Wherein, described solute is LiPF6It is molten
Liquid and NaPF6Solution, described mixed solvent are EC, DMC and EMC.
10. the half-cell according to claim 8 containing lithium/sodium double ion manganese-base oxide positive electrode, its feature exist
In：
Described LiPF6The concentration of solution is 1mol/L；
Described NaPF6The concentration of solution is 1mol/L；
Described LiPF6Solution and NaPF6The volume ratio of solution is 1~11：1；
Described EC, DMC and EMC volume ratio is 1：1：1.
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| CN108615932A (en) * | 2018-03-30 | 2018-10-02 | 南京大学 | Negative and positive double ion rocking chair type secondary cell and preparation method thereof |
| CN110098405A (en) * | 2019-03-22 | 2019-08-06 | 长沙理工大学 | A kind of preparation method of anode material for lithium ion battery |
| CN110336010A (en) * | 2019-07-10 | 2019-10-15 | 河南师范大学 | The preparation method of the miscellaneous nanoscale sodium-ion battery positive material of cation-anion co-doping with strong interaction |
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