CN107123789A - A kind of lithium-rich manganese-based composite, its preparation method and its application - Google Patents
A kind of lithium-rich manganese-based composite, its preparation method and its application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides lithium-rich manganese-based composite of the one kind as shown in formula (I), present invention also provides the preparation method of the lithium-rich manganese-based composite, comprise the following steps：Material as shown in formula (II), the lithium-rich manganese base material as shown in formula (III) are mixed with additive, mixing material, one or more of the additive in citric acid, glucose, chitosan and sucrose is obtained；The mixing material is heat-treated, the lithium-rich manganese-based composite as shown in formula (I) is obtained.Lithium-rich manganese-based composite prepared by the application has the features such as excellent cycle performance and improved voltage drop.In addition, this method process engineering is simple, it is easy to accomplish industrialization；LiαZβ(PO4)γ/xLi2MnO3·(1‑x)LiMO2(I)。
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of lithium-rich manganese-based composite wood
Material, its preparation method and its application.
Background technology
Lithium ion battery has the advantages that high-energy, long-life and memory-less effect, is considered as
It is most potential Prospect of EVS Powered with Batteries.However, the property of current dynamic lithium battery
The demand in market, especially one of crucial performance indications high-energy can be not met by with cost
Density.The energy density for improving battery essentially consists in the energy density for improving electrode material, and carries
The energy density of high electrode material is mainly improved two ways of specific capacity and operating voltage of material
Footpath.So far commercial positive electrode includes cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material and phosphorus
Sour iron lithium, but the actual specific capacity of above-mentioned electrode material is generally less than 200mAh g-1, up to not
To the requirement of electrokinetic cell, therefore, in the urgent need to research more height ratio capacity, more inexpensive and more
Long-life novel anode material.
Lithium-rich manganese-based anode material is because its specific discharge capacity is up to 300mAh g-1And it is relatively low into
Originally have been a great concern.But it is low, forthright again that this material has first charge-discharge efficiency
Can poor, cycle performance difference and the shortcomings of voltage drop, it is necessary to pass through the method for modifying of cladding or doping
To solve.For example, Application No. 201210194840.7 and Application No. 2014104001325.0
Chinese patent the cycle performance of lithium-rich manganese-based anode material is improved by coated metal oxide
And high rate performance；The Chinese patent of Application No. 201410522684.1 is by preparing presoma
During it is chromium-doped after coat lithium carbonate again and improve discharge capacity, cycle performance and high rate performance.
Although phosphate system positive electrode is relatively low compared to lithium-rich manganese-based anode material specific capacity,
There is absence of voltage, the researcher such as Qiao is using the method for spray drying by LiMnPO4
Lithium-rich manganese-based anode material surface is coated to, obtained material modified high rate performance and cyclicity
It can be improved.But this method technique is complex, higher is mutually required to material thing, and to richness
The voltage drop of lithium manganese-based anode material is not obviously improved.
The content of the invention
Present invention solves the technical problem that being to provide a kind of lithium-rich manganese-based composite, its conduct
The positive electrode of lithium ion battery has good cycle performance and voltage drop.
In view of this, the lithium-rich manganese-based composite wood this application provides one kind as shown in formula (I)
Material,
LiαZβ(PO4)γ/xLi2MnO3·(1-x)LiMO2(Ⅰ)；
Wherein, 1≤α≤3,1≤β≤2,1≤γ≤3, α, β and γ are natural number；
One or more of the Z in Fe, Mn, Ni, Co and V；
0 ＜ x ＜ 1, one or more of the M in Ni, Co, Mn and Al.
It is preferred that, the LiαZβ(PO4)γWith xLi2MnO3·(1-x)LiMO2Mass ratio be
(0.01~0.8):(0.2~0.99).
It is preferred that, the LiαZβ(PO4)γSelected from monoclinic form LiZPO4, three oblique crystal formations
Li3Z2(PO4)2One or more.
It is preferred that, the monoclinic form LiZPO4Selected from LiVPO4、LiCoPO4Or LiNiPO4,
The three oblique crystal formation Li3Z2(PO4)2Selected from Li3V2(PO4)2。
Present invention also provides the preparation of lithium-rich manganese-based composite of the one kind as shown in formula (I)
Method, comprises the following steps：
By the material as shown in formula (II), the lithium-rich manganese base material as shown in formula (III) with adding
Plus agent mixing, mixing material is obtained, the additive is selected from citric acid, glucose, chitosan
With the one or more in sucrose；
The mixing material is heat-treated, obtains lithium-rich manganese-based multiple as shown in formula (I)
Condensation material；
LiαZβ(PO4)γ/xLi2MnO3·(1-x)LiMO2(Ⅰ)；
LiαZβ(PO4)γ(Ⅱ)；
xLi2MnO3·(1-x)LiMO2(Ⅲ)；
Wherein, 1≤α≤3,1≤β≤2,1≤γ≤3, α, β and γ are natural number；
One or more of the Z in V, Ni and Co；
0 ＜ x ＜ 1, one or more of the M in Ni, Co, Mn and Al.
It is preferred that, the material as shown in formula (II) and the richness as shown in formula (III)
The mass ratio of lithium Mn-based material is (0.01~0.8)：(0.2~0.99).
It is preferred that, the material as shown in formula (II) and the richness as shown in formula (III)
The ratio of the gross mass of lithium Mn-based material and the quality of the additive is 1:(0.01~0.1), it is excellent
Elect 1 as:(0.02~0.05).
It is preferred that, the heat treatment is carried out under protective atmosphere, and the protective atmosphere is nitrogen
Gas, argon gas or carbon dioxide, the temperature of the heat treatment is 200~500 DEG C, the heat treatment
Time be 1~5h.
It is preferred that, the mode of the mixing is solid phase mixing, and the time of the mixing is small more than 1
In equal to 5h.
Present invention also provides the lithium-rich manganese-based composite described in such scheme or such scheme
Lithium-rich manganese-based composite prepared by described preparation method is on anode material for lithium-ion batteries
Application.
This application provides lithium-rich manganese-based composite of the one kind as shown in formula (I), it will be as
Phosphate system material shown in formula (II), the lithium-rich manganese base material as shown in formula (III) with
It is heat-treated after additive mixing, and has obtained lithium-rich manganese-based compound as shown in formula (I)
Material.It is carbon containing to add under heat treatment condition during lithium-rich manganese-based composite is prepared
Plus agent sinters to form conductive carbon, it is scattered between lithium-rich manganese base material and phosphate system, especially
It is the rearrangement work of the top layer generation ion exchange formula for the top layer and phosphoric acid vanadium lithium for promoting rich lithium material
With, make material have the special performance different from Surface coating, the electro-chemical activity of material with
The diffusion rate of body phase lithium ion, thus improve the cycle performance of lithium-rich manganese-based composite with
Voltage attenuation.
Brief description of the drawings
Fig. 1 is lithium-rich manganese-based composite and lithium-rich manganese-based anode prepared by the embodiment of the present invention 1
Material and Li3V2PO4Cycle performance compare figure；
Fig. 2 is lithium-rich manganese-based composite and lithium-rich manganese-based anode prepared by the embodiment of the present invention 1
Material and Li3V2PO4Voltage drop compare figure.
Embodiment
For a further understanding of the present invention, with reference to embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these descriptions are simply the feature for further illustrating the present invention
And advantage, rather than limiting to the claimed invention.
The embodiment of the invention discloses lithium-rich manganese-based composite of the one kind as shown in formula (I),
LiαZβ(PO4)γ/xLi2MnO3·(1-x)LiMO2(Ⅰ)；
Wherein, 1≤α≤3,1≤β≤2,1≤γ≤3, α, β and γ are natural number；
One or more of the Z in V, Ni and Co；
0 ＜ x ＜ 1, one or more of the M in Ni, Co, Mn and Al.
Li in herein described lithium-rich manganese-based compositeαZβ(PO4)γFor phosphate system material
Material, it is preferably selected from monoclinic form LiZPO4With three oblique crystal formation Li3Z2(PO4)2One kind or many
Kind, in embodiment, the LiαZβ(PO4)γMore preferably Li3V2(PO4)3、LiVPO4、
LiNiPO4Or LiCoPO4。
The LiαZβ(PO4)γWith xLi2MnO3·(1-x)LiMO2Mass ratio be preferably
(0.01~0.8):(0.2~0.99), more preferably (0.1~0.6)：(0.4~0.95), is implementing
In example, more preferably (0.1~0.5)：(0.5~0.9).
Present invention also provides the preparation of lithium-rich manganese-based composite of the one kind as shown in formula (I)
Method, comprises the following steps：
By the material as shown in formula (II), the lithium-rich manganese base material as shown in formula (III) with adding
Plus agent mixing, mixing material is obtained, the additive is selected from citric acid, glucose, chitosan
With the one or more in sucrose；
The mixing material is heat-treated, obtains lithium-rich manganese-based multiple as shown in formula (I)
Condensation material；
LiαZβ(PO4)γ/xLi2MnO3·(1-x)LiMO2(Ⅰ)；
LiαZβ(PO4)γ(Ⅱ)；
xLi2MnO3·(1-x)LiMO2(Ⅲ)；
Wherein, 1≤α≤3,1≤β≤2,1≤γ≤3, α, β and γ are natural number；
One or more of the Z in V, Ni and Co；
0 ＜ x ＜ 1, one or more of the M in Ni, Co, Mn and Al.
Herein described LiαZβ(PO4)γWith xLi2MnO3·(1-x)LiMO2According to existing side
It is prepared by method.
During lithium-rich manganese-based composite is prepared, first by the material as shown in formula (II)
Material, the lithium-rich manganese base material as shown in formula (III) are mixed with additive, obtain mixing material.
Described to be mixed into solid phase mixing, the time of the mixing is more than 0 and is less than or equal to 5h.It is described
LiαZβ(PO4)γIt is preferably selected from monoclinic form LiNPO4With three oblique crystal formation Li3N2(PO4)2One kind
Or it is a variety of, in embodiment, the LiαZβ(PO4)γMore preferably Li3V2(PO4)3、LiVPO4、
LiNiPO4Or LiCoPO4；X in the lithium-rich manganese base material as described in formula (II) is excellent
Elect 0.4 or 0.5 as, one or more of the M in Ni, Co, Mn and Al, its
When middle M is selected from different elements, the subscript sum of each element is equal to 1；Described in embodiment
Lithium-rich manganese base material is more preferably 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2、
0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2、
0.5Li2MnO3·0.5LiNi0.4Co0.2Mn0.4O2、
0.4Li2MnO3·0.6LiNi0.5Co0.2Mn0.3O2、0.4Li2MnO3·0.6LiNi0.8Co0.1Mn0.1O2
Or 0.4Li2MnO3·0.6LiNi0.82Co0.13Al0.05O2。
According to the present invention, the material as shown in formula (II) with it is described as shown in formula (III)
Lithium-rich manganese base material mass ratio be (0.01~0.8)：(0.99~0.2).Above two material
Specific capacity difference it is larger can then produce influence to the capacity of lithium-rich manganese-based anode material, but such as
The addition of material shown in formula (II) can improve cycle performance and the reduction circulation of composite
During voltage drop.The material as shown in formula (II) with it is described as shown in formula (III)
Lithium-rich manganese base material gross mass and the additive quality ratio be 1:(0.01~0.1),
In embodiment, more preferably 1:(0.02~0.05).
The one kind of herein described additive in citric acid, glucose, chitosan and sucrose
Or it is a variety of, in embodiment, the additive be more preferably glucose, chitosan, sucrose or
Citric acid；It is cracked into conductive carbon under high temperature action and is scattered in lithium-rich manganese base material
xLi2MnO3·(1-x)LiMO2With LiαNβ(PO4)γInside particle and between particle, so as to improve
The electro-chemical activity and the diffusion rate of body phase lithium ion of composite material surface.
Then obtained mixing material is heat-treated by the application, obtains lithium-rich manganese-based composite wood
Material.The heat treatment will the mixing material carry out high temperature sintering, split additive therein
Solution forms conductive carbon, is scattered in lithium-rich manganese-based anode material xLi2MnO3·(1-x)LiMO2With
LiαNβ(PO4)γInside particle and between particle, to improve the performance of lithium-rich manganese-based composite.
The temperature of the heat treatment is preferably 200~500 DEG C, and the time of the heat treatment is 1~5h.Institute
State heat treatment to carry out preferably under protective atmosphere, the protective atmosphere is preferably nitrogen, argon
Gas or carbon dioxide.
Present invention also provides the lithium-rich manganese-based composite or prepared lithium-rich manganese-based multiple
Application of the condensation material on anode material for lithium-ion batteries.
The application is during lithium-rich manganese-based composite is prepared, first by lithium-rich manganese-based material
Material, LiαNβ(PO4)γMix, then be heat-treated with additive；In high-temperature sintering process,
Lithium-rich manganese-based anode material xLi2MnO3·(1-x)LiMO2With LiαNβ(PO4)γPhase between two-phase
Interaction, forms solid phase ion conductor, and additive cracking obtains conductive carbon, is scattered in rich lithium manganese
Base anode material xLi2MnO3·(1-x)LiMO2With LiαNβ(PO4)γInside particle and particle it
Between, so as to improve the electro-chemical activity and body phase lithium ion of lithium-rich manganese-based composite material surface
Diffusion rate.
For a further understanding of the present invention, the rich lithium manganese provided with reference to embodiment the present invention
Based composites, its preparation method and its application are described in detail, protection scope of the present invention
It is not limited by the following examples.
Embodiment 1
(1) by 0.7kg lithium-rich manganese base materials 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2、
The oblique crystal formation Li of 0.3kg tri-3V2(PO4)3Mixer-mill batch mixing 3h is used with 30g glucose, is mixed
Material；
(2) above-mentioned mixing material is placed in argon atmosphere, anneal 3h in 400 DEG C, obtains
To the lithium-rich manganese-based composite positive pole that formula is (IV)；
Li3V2(PO4)3/0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 (Ⅳ)。
Embodiment 2
(1) by 0.5kg lithium-rich manganese base materials 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2、
The oblique crystal formation Li of 0.5kg tri-3V2(PO4)3With 40g chitosans mixer-mill batch mixing 3h, mixing material is obtained
Material；
(2) above-mentioned mixing material is placed in argon atmosphere, anneal 3h in 450 DEG C, obtains
To the lithium-rich manganese-based composite positive pole that formula is (IV)；
Li3V2(PO4)3/0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 (Ⅳ)。
Embodiment 3
(1) by 0.6kg lithium-rich manganese base materials 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2、
0.4kg monoclinic forms LiVPO4With 30g glucose mixer-mill batch mixing 2h, mixing material is obtained；
(2) above-mentioned mixing material is placed in argon atmosphere, anneal 4h in 400 DEG C, obtains
To the lithium-rich manganese-based composite positive pole that formula is (V)；
LiVPO4/0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2 (Ⅴ)。
Embodiment 4
(1) by 0.8kg lithium-rich manganese base materials 0.5Li2MnO3·0.5LiNi0.4Co0.2Mn0.4O2、
0.2kg olivine crystal formations LiNiPO4With 40g sucrose mixer-mill batch mixing 4h, mixing material is obtained；
(2) above-mentioned mixing material is placed in argon atmosphere, anneal 3h in 450 DEG C, obtains
To the lithium-rich manganese-based composite positive pole that formula is (VI)；
LiNiPO4/0.5Li2MnO3·0.5LiNi0.4Co0.2Mn0.4O2 (Ⅵ)。
Embodiment 5
(1) by 0.5kg lithium-rich manganese base materials 0.4Li2MnO3·0.6LiNi0.5Co0.2Mn0.3O2、
0.5kg olivine crystal formations LiCoPO4With 50g citric acids mixer-mill batch mixing 3h, mixing material is obtained
Material；
(2) mixing material is placed in argon atmosphere, anneal 3h in 470 DEG C, is led to
Formula is the lithium-rich manganese-based composite positive pole of (VII)；
LiCoPO4/0.4Li2MnO3·0.6LiNi0.5Co0.2Mn0.3O2 (Ⅶ)。
Embodiment 6
(1) by 0.9kg lithium-rich manganese base materials 0.4Li2MnO3·0.6LiNi0.8Co0.1Mn0.1O2、
The oblique crystal formation Li of 0.1kg tri-3V2(PO4)3With 20g sucrose mixer-mill batch mixing 4h, mixing material is obtained；
(2) above-mentioned mixing material is placed in argon atmosphere, anneal 4h in 390 DEG C, obtains
To the lithium-rich manganese-based composite positive pole that formula is (VIII)；
Li3V2(PO4)3/0.4Li2MnO3·0.6LiNi0.8Co0.1Mn0.1O2 (Ⅷ)。
Embodiment 7
(1) by 0.8kg lithium-rich manganese base materials 0.4Li2MnO3·0.6LiNi0.82Co0.13Al0.05O2、
0.2kg monoclinic forms LiVPO4With 30g glucose mixer-mill batch mixing 2h, mixing material is obtained；
(2) above-mentioned mixing material is placed in argon atmosphere, anneal 3h in 400 DEG C, obtains
To the lithium-rich manganese-based composite positive pole that formula is (Ⅸ)；
LiVPO4/0.4Li2MnO3·0.6LiNi0.82Co0.13Al0.05O2 (Ⅸ)。
Comparative example 1
By the lithium-rich manganese-based composite 0.4Li of 0.7kg2MnO3·0.6LiNi1/3Co1/3Mn1/3O2、
The oblique crystal formation Li of 0.3kg tri-3V2(PO4)3With mixer-mill batch mixing 3h, it is (II) rich lithium manganese to obtain formula
Base composite positive pole；
Li3V2(PO4)3/0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 (Ⅳ)。
It is lithium-rich manganese-based composite positive pole 0.8g prepared by embodiment 1, conductive carbon black 0.5g, poly-
Vinylidene 0.5g and 1-METHYLPYRROLIDONE 30g are mixed to form slurry at normal temperatures and pressures, uniformly
Aluminium foil surface is coated in, pole piece is obtained；Compress, cut after the pole piece is dried at 80 DEG C
It is 1.32cm into area2Thin rounded flakes as positive pole, using pour lithium slice as negative pole, with 1mol/L's
LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) solution be electrolyte, its
In, EC and DMC volume ratio are 7:3, button lithium is assembled into the glove box full of argon gas
Ion battery.By obtained lithium-rich manganese-based composite in comparative example 1 be made in the same way lithium from
Sub- battery.
Cycle performance test, test temperature are carried out to the lithium ion battery using LAND testers
Spend for 25 DEG C, charging and discharging currents are 50mA/g, charge cutoff voltage is 4.8V, electric discharge cut-off
Voltage is 2.0V, as a result referring to accompanying drawing 1 and accompanying drawing 2.■ curves are lithium-rich manganese-based material in Fig. 1
The cycle performance curve of material, ● curve is following for lithium-rich manganese-based composite prepared by embodiment 1
Ring performance curve, zero curve is the cycle performance of lithium-rich manganese-based composite prepared by comparative example 1
Curve, △ curves are Li3V2(PO4)3Cycle performance curve；As shown in Figure 1, present invention system
The cycle performance of standby lithium-rich manganese-based composite positive pole be substantially better than lithium-rich manganese-based anode material and
Li3V2(PO4)3Material.■ curves are the falloff curve of lithium-rich manganese base material in Fig. 2, ● curve
The falloff curve of the lithium-rich manganese-based composite prepared for embodiment 1, zero curve is comparative example 1
The falloff curve of the lithium-rich manganese-based composite prepared, △ curves are Li3V2(PO4)3Pressure drop it is bent
Line；As shown in Figure 2, during charge and discharge cycles, the lithium-rich manganese-based anode composite material of preparation
The voltage drop that material is produced is less than lithium-rich manganese-based anode material and Li3V2(PO4)3Material.Therefore originally
The cycle performance for inventing the lithium-rich manganese-based composite prepared is improved, and voltage drop is obtained
Suppress.
The explanation of above example is only intended to help the method and its core that understand the present invention to think
Think.It should be pointed out that for those skilled in the art, not departing from this hair
On the premise of bright principle, some improvement and modification can also be carried out to the present invention, these improve and
Modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize
Or use the present invention.A variety of modifications to these embodiments come to those skilled in the art
Say and will be apparent, generic principles defined herein can not depart from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and is to fit to and principles disclosed herein and new
The consistent most wide scope of clever feature.
Claims (10)
1. a kind of lithium-rich manganese-based composite as shown in formula (I),
LiαZβ(PO4)γ/xLi2MnO3·(1-x)LiMO2(I)；
Wherein, 1≤α≤3,1≤β≤2,1≤γ≤3, α, β and γ are natural number；
One or more of the Z in Fe, Mn, Ni, Co and V；
0 ＜ x ＜ 1, one or more of the M in Ni, Co, Mn and Al.
2. lithium-rich manganese-based composite according to claim 1, it is characterised in that institute
State LiαZβ(PO4)γWith xLi2MnO3·(1-x)LiMO2Mass ratio be (0.01~0.8):
(0.2~0.99).
3. lithium-rich manganese-based composite according to claim 1, it is characterised in that institute
State LiαZβ(PO4)γSelected from monoclinic form LiZPO4, three oblique crystal formation Li3Z2(PO4)2One kind or
It is a variety of.
4. lithium-rich manganese-based composite according to claim 1, it is characterised in that institute
State monoclinic form LiZPO4Selected from LiVPO4、LiCoPO4Or LiNiPO4, described three is tiltedly brilliant
Type Li3Z2(PO4)2Selected from Li3V2(PO4)2。
5. a kind of preparation method of lithium-rich manganese-based composite as shown in formula (I), including
Following steps：
By the material as shown in formula (II), the lithium-rich manganese base material as shown in formula (III) with adding
Plus agent mixing, mixing material is obtained, the additive is selected from citric acid, glucose, chitosan
With the one or more in sucrose；
The mixing material is heat-treated, obtains lithium-rich manganese-based multiple as shown in formula (I)
Condensation material；
LiαZβ(PO4)γ/xLi2MnO3·(1-x)LiMO2(I)；
LiαZβ(PO4)γ(Ⅱ)；
xLi2MnO3·(1-x)LiMO2(Ⅲ)；
Wherein, 1≤α≤3,1≤β≤2,1≤γ≤3, α, β and γ are natural number；
One or more of the Z in V, Ni and Co；
0 ＜ x ＜ 1, one or more of the M in Ni, Co, Mn and Al.
6. preparation method according to claim 5, it is characterised in that described such as formula (II)
Shown material and the mass ratio of the lithium-rich manganese base material as shown in formula (III) are
(0.01~0.8)：(0.2~0.99).
7. preparation method according to claim 5, it is characterised in that described such as formula (II)
Shown material and the gross mass of the lithium-rich manganese base material as shown in formula (III) add with described
Plus the ratio of the quality of agent is 1:(0.01~0.1), preferably 1:(0.02~0.05).
8. preparation method according to claim 5, it is characterised in that the heat treatment
Carried out under protective atmosphere, the protective atmosphere is nitrogen, argon gas or carbon dioxide, institute
The temperature for stating heat treatment is 200~500 DEG C, and the time of the heat treatment is 1~5h.
9. preparation method according to claim 5, it is characterised in that the mixing
Mode is solid phase mixing, and the time of the mixing is more than 1 and is less than or equal to 5h.
10. lithium-rich manganese-based composite or claim 5~9 described in any one of Claims 1 to 4
Lithium-rich manganese-based composite prepared by preparation method described in any one is in lithium ion cell positive
Application on material.
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