CN106935808A - Positive electrode active materials and preparation method thereof and cell size and positive pole and lithium battery - Google Patents
Positive electrode active materials and preparation method thereof and cell size and positive pole and lithium battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a kind of positive electrode active materials and preparation method thereof and cell size and positive pole and lithium battery.Wherein, positive electrode active materials have core shell structure, and core portion is with LiMnxFe1-xPO4The active component of/C-structure, 0 ＜ x ＜ 1；Shell is coated on the surface in the core portion, is the LiFePO4 compound-material layer that outer surface coats carbon-coating.The positive electrode active materials are by with LiMnxFe1-xPO4The active component outside of/C-structure forms the LiFePO4 compound-material layer that outer surface coats carbon-coating, the content of Magnetic Materials in prepared positive electrode active materials can be effectively reduced, and then improve battery in use, the easy self discharge of negative material, the not good problem of cycle performance, and improve the service life of battery.
Description
Technical field
The present invention relates to lithium battery preparation field, in particular it relates to a kind of positive-active material
Material；The invention further relates to a kind of preparation method of aforementioned positive electrode active material；The present invention is also further related to
And a kind of cell size for including aforementioned positive electrode active material, and including aforementioned positive electrode active material
Positive pole, and the lithium battery including the positive pole.
Background technology
Lithium rechargeable battery is novel green high-power rechargeable battery, and it has, and voltage is high, energy density
The many merits such as greatly, good cycle, small self discharge, memory-less effect, working range be wide, extensively should
For mobile phone, notebook computer, portable power tool, electronic instrument, weaponry etc., in electricity
Also had a good application prospect in electrical automobile, the weight that countries in the world competitively research and develop has been turned at present
Point.Positive pole is a critically important part of lithium ion battery, in lithium ion battery charge and discharge process,
Reciprocal embedding/de- required lithium in positive and negative lithium intercalation compound to be not only provided, and also provides negative pole material
Material surface form SEI films required for lithium, therefore, research and develop high performance positive electrode be lithium from
The key point of sub- battery development.
In lithium ion cell positive, iron manganese phosphate for lithium shows optimal in combination property, is presently considered to
It is ideal lithium ion secondary power battery positive electrode.The preparation of existing iron manganese phosphate for lithium product
Method is mainly high temperature solid-state method, and its processing step includes：(1) by manganese source and phosphorus source according to mol ratio 1：
1 is synthesized manganese phosphate, and washing is dried to obtain stratum nucleare manganese phosphate presoma；(2) by step (1) stratum nucleare
Manganese phosphate presoma is dispersed in water, wiring solution-forming A；(3) source of iron is dissolved in water, wiring solution-forming B；
(4) solution B in step (3) is added in the solution A in step (2), in nitrogen protection
Under, stir and heating response, after washing is dried, obtain nucleocapsid ferrous phosphate manganese presoma；(5) weigh
Li source compound and step (4) nucleocapsid phosphoric acid Asia ferromanganese presoma, before lithium source and ferrous phosphate manganese
It is 1.0-1.2 to drive body mol ratio：1 ratio is well mixed, and the carbon source of 5%-13% is added in the mixture,
250-500 DEG C is heated in nitrogen atmosphere, and 2-8h is persistently calcined at 250-500 DEG C, be subsequently cooled to
Room temperature, obtains nucleocapsid ferrous phosphate manganese lithium presoma；(6) the ferrous phosphate manganese for obtaining step (5)
Lithium presoma is crushed, and continuation is heated to 700-900 DEG C in nitrogen atmosphere, and is held under 700-900 degree
Continuous calcining 5-20h, is subsequently cooled to room temperature, can obtain ferrous phosphate manganese lithium material.
Although iron manganese phosphate lithium material can be used as lithium ion battery synthesized by existing high temperature solid-state method
Electrode material, however, with the extensive use of lithium rechargeable battery, consumer is for lithium ion secondary
The performance of battery, such as high temperature cyclic performance propose requirement higher.How electricity is further improved
The high temperature cyclic performance in pond, has become the research emphasis that lithium rechargeable battery researches and develops field.
The content of the invention
It is an object of the invention to provide a kind of positive electrode active materials and preparation method thereof and positive pole and lithium electricity
Pond, to improve the high temperature cyclic performance of battery.
To achieve these goals, according to an aspect of the present invention, there is provided a kind of positive-active material
Material, the positive electrode active materials have core shell structure, wherein, core portion is with LiMnxFe1-xPO4/ C is tied
The active component of structure, 0 ＜ x ＜ 1；Shell is coated on the surface in the core portion, is outer surface cladding carbon-coating
LiFePO4 compound-material layer.
According to the second aspect of the invention, there is provided a kind of preparation side of above-mentioned positive electrode active materials
Method, the preparation method is comprised the following steps：S1, offer have LiMnxFe1-xPO4The activity of/C-structure
Component；S2, under hydrothermal synthesizing condition, described will have LiMnxFe1-xPO4The activearm of/C-structure
Point mixing contact in a solvent with the first lithium source, the first source of iron, the first phosphorus source and the first carbon source forms institute
State positive electrode active materials.
According to the third aspect of the present invention, there is provided a kind of positive electrode active materials, the positive-active material
Material is prepared from by above-mentioned preparation method of the invention.
According to the fourth aspect of the present invention, there is provided a kind of cell size, the cell size includes
Positive electrode active materials and solvent, the positive electrode active materials are above-mentioned positive electrode active materials of the invention.
According to the fifth aspect of the present invention, there is provided a kind of positive pole, the positive pole includes collector and sets
The anode active material layer on the collector is put, the anode active material layer is including the present invention just
Pole active material.
According to the sixth aspect of the invention, there is provided a kind of lithium battery, the lithium battery interior is equipped with
Positive pole, the positive pole includes above-mentioned positive pole.
Positive electrode active materials provided by the present invention, by with LiMnxFe1-xPO4The work of/C-structure
Property component surface further formed outer surface coat carbon-coating LiFePO4 compound-material layer, can
The content of Magnetic Materials in material is effectively reduced, and then causes the positive pole made by the positive electrode active materials
After the full electricity state high temperature storages of the battery 4.3V of making, stain quantity is less than 10 on negative material surface
/cm2, so that improve battery in use, and the easy self discharge of negative material, high temperature cyclic performance is not
Good problem, to improve the service life of battery.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explain the present invention, and is not intended to limit the invention.
It is directed to " positive pole made by existing iron manganese phosphate lithium material, electricity pointed by background section
The high temperature cyclic performance in pond need further raising " problem.The present inventor is to iron manganese phosphate for lithium
Positive pole and preparation method thereof, and the application of battery has carried out substantial amounts of research, in once accidental machine
Under meeting, inventor has found Magnetic Materials (the magnetic material of tool) in positive pole prepared by iron manganese phosphate for lithium class material
Content it is higher when, after the full electricity state high temperature storage of prepared battery 4.3V, on negative material surface
Stain quantity is more, typically larger than 20/cm2.Exactly because stain number on possible negative material surface
Amount is more to cause it easily to produce self discharge, and then may influence the cycle performance of meeting battery and use
Life-span.
Discovery based on this technical problem, the present inventor again to iron manganese phosphate for lithium class just
Pole and preparation method thereof, and the application of battery has carried out substantial amounts of research, and of the invention
On one side, it is proposed that a kind of positive electrode active materials.The positive electrode active materials have core shell structure, its
In, core portion is with LiMnxFe1-xPO4The active component of/C-structure, 0 ＜ x ＜ 1；Shell is coated on core
The surface in portion, is the LiFePO4 compound-material layer of outer surface cladding carbon-coating.
The positive electrode active materials are followed successively by LiMn from inside to outside in the present inventionxFe1-xPO4Particle,
One carbon-coating, LiFePO4 compound-material layer, the second carbon-coating.The present invention " has LiMnxFe1-xPO4/C
The active component of structure " is carbon coating iron manganese phosphate lithium material.The above-mentioned positive electrode active materials of the present invention, lead to
Cross with LiMnxFe1-xPO4The surface of the active component of/C-structure further forms outer surface carbon coated
The LiFePO4 compound-material layer of layer, can be effectively reduced containing for Magnetic Materials in positive electrode active materials
Amount, and then cause that the full electricity states of battery 4.3V that the positive pole made by the positive electrode active materials makes are high gentle
After storage, stain quantity is less than 10/cm on negative material surface2.Used so as to improve battery
Cheng Zhong, the easy self discharge of negative material, the not good problem of cycle performance improves the service life of battery.
According to above-mentioned positive electrode active materials provided by the present invention, as long as with LiMnxFe1-xPO4/C
The surface of the active component of structure forms the LiFePO4 compound-material layer that outer surface coats carbon-coating, just
The content of Magnetic Materials in prepared positive electrode active materials can be reduced in certain degree, electricity is improved
The high temperature cyclic performance in pond.However, the cycle performance in order to further optimize battery, according to the present invention
One side, in above-mentioned positive electrode active materials the content of Magnetic Materials be 700-850 weight ppm, according to
There is LiMn described in another aspect of the present inventionxFe1-xPO4Magnetic Materials in the active component of/C-structure
Content is 900-1150 weight ppm.It is to use JSII-G1 in the content of Magnetic Materials involved in the present invention
Magnetic Materials analyzer carries out test acquisition.
According to above-mentioned positive electrode active materials provided by the present invention, the thickness of particle diameter and shell for core portion
Degree does not have particular/special requirement, as long as shell can integrally be wrapped in core portion surface.Preferably, have
There is LiMnxFe1-xPO4The particle diameter D of the active component of/C-structure50It is 100-500nm；The appearance bread
The radial thickness for covering the LiFePO4 compound-material layer of carbon-coating is 5-25nm.By above-mentioned positive-active material
The thickness of material core portion and shell is limited within the above range, is conducive to keeping phosphoric acid Asia ferromanganese lithium material
While high-energy-density in low material Magnetic Materials content.
According to above-mentioned positive electrode active materials provided by the present invention, for having positioned at core portion
LiMnxFe1-xPO4The content of iron and manganese does not have particular/special requirement in the active component of/C-structure, however,
In order to optimize the energy density performance of positive electrode active materials, preferably with LiMnxFe1-xPO4/ C-structure
0.5≤x ＜ 1 in active component.Simultaneously for LiMnxFe1-xPO4In the active component of/C-structure
The content of carbon does not have particular/special requirement yet, however, the electric conductivity in order to optimize positive electrode active materials,
It is preferably based on LiMnxFe1-xPO4The gross weight of the active component of/C-structure, it is described to have
LiMnxFe1-xPO4Carbon content is 1.5-3wt% in the active component of/C-structure.
According to above-mentioned positive electrode active materials provided by the present invention, for being coated positioned at the outer surface of shell
The consumption of each element does not have particular/special requirement in the LiFePO4 compound-material layer of carbon-coating, as long as can
Embody the content of corresponding Magnetic Materials.Preferred outer surface coats the ferric phosphate of carbon-coating in the present invention
Phosphorus, iron, the mol ratio of lithium are 1 in lithium compound material layer：1：0.9-1.1, is preferably based on outer surface
The gross weight of the LiFePO4 compound-material layer of carbon-coating is coated, outer surface coats the LiFePO4 of carbon-coating
Carbon content is 1.5-3wt% in compound-material layer.
According to above-mentioned positive electrode active materials provided by the present invention, for containing for active component and clad
Amount does not have particular/special requirement, as long as the LiFePO4 compound-material layer for coating carbon-coating is coated on into activearm
Point surface just can to a certain extent realize the purpose of the present invention, in the present invention the preferred positive-active
There is LiMn in materialxFe1-xPO4The active component of/C-structure coats the phosphorus of carbon-coating in terms of phosphorus with outer surface
Sour iron lithium compound material layer with the mol ratio that phosphorus is counted be 1：(0.05-0.3), preferably 1：
(0.1-0.2)。
According to the second aspect of the invention, a kind of preparation method of positive electrode active materials is additionally provided,
The preparation method is comprised the following steps：S1, offer have LiMnxFe1-xPO4The activearm of/C-structure
Point；S2, under hydrothermal synthesizing condition, described will have LiMnxFe1-xPO4The active component of/C-structure
Mix in a solvent with the first lithium source, the first source of iron, the first phosphorus source and the first carbon source and contact, to be formed
State positive electrode active materials.
The above method provided by the present invention, can have by simple Hydrothermal Synthesiss
LiMnxFe1-xPO4The surface of the active component of/C-structure forms relatively uniform outer surface cladding carbon-coating
LiFePO4 compound-material layer, can be effectively reduced the content of Magnetic Materials in material, and then makes
Obtain after the full electricity state high temperature storages of battery 4.3V that the positive pole made by the positive electrode active materials makes, bear
Stain quantity is less than 10/cm on the material surface of pole2.So as to improve battery in use, negative pole
The easy self discharge of material, the not good problem of cycle performance, and improve the service life of battery.
In the above method provided by the present invention, for being provided with LiMnxFe1-xPO4/ C-structure
Active component do not have particular/special requirement, it can be commercially available prod, or made products.
The content for providing Magnetic Materials in the present invention in the preferred S1 is the activity of 900-1150 weight ppm
Component, it is preferable that the particle diameter D of the active component50It is 100-500nm, more preferably active component
In, 0.5≤x ＜ 1, carbon content is 1.5-3wt% in particularly preferred active component.
In the above method provided by the present invention, provided with LiMnxFe1-xPO4The work of/C-structure
Property component if made products, then for formed have LiMnxFe1-xPO4The active component of/C-structure
Technique do not have specific requirement, for example can be using high temperature solid-state method, hydro-thermal method etc., these works
Process is referred to ordinary skill in the art means.High temperature solid-state is preferably used in the present invention
Method synthesizes, and has LiMn using high temperature solid-state method synthesisxFe1-xPO4The active component of/C-structure, has
The advantage of good conductivity.
Preparation method provided by the present invention is further illustrated below with reference to high temperature solid-state method.
In the preparation method of positive electrode active materials provided by the present invention, S1 is comprised the following steps：S11、
Second lithium source, the second source of iron, manganese source, the second phosphorus source and second carbon source are mixed in proportion, before acquisition
Drive somaplasm material；S12, the precursor pulp is sequentially passed through spray drying, sintering formed described in have
LiMnxFe1-xPO4The active component of/C-structure, second phosphorus source is identical with first phosphorus source or not
Together, second source of iron and the first source of iron are identical or different, and second lithium source is identical with the first lithium source
Or it is different, the second carbon source and the first carbon source are identical or different.Wherein：
In step s 11, by the second lithium source in terms of lithium, the second source of iron and manganese source are with iron and the total amount of manganese
Meter, the second phosphorus source is in molar ratio (0.9-1.1) in terms of phosphorus:1:1 mixing, and add foregoing final institute's shape
Into outer surface cladding carbon-coating LiFePO4 compound-material layer in carbon content for 1.5wt%-3wt%
Carbon source, then by resulting mixture, obtains precursor pulp.It is identical with this area conventional method,
The carbon source added in the present invention, can be enriched to iron manganese phosphate for lithium class material during sintering processes
Surface, therefore formed have LiMnxFe1-x-yMyPO4/ C-structure, the i.e. iron manganese phosphate of carbon coating structure
Lithium class material.
In a kind of relative specific embodiment of the invention, above-mentioned steps S11 includes：(1) adopt
The second lithium source is made into (0.1-2.0) molL with deionized water-1Solution；(2) the second phosphorus source is used
It is made into (0.1-2.0) molL-1Solution；(3) manganese source is made into (1.0-2.0) using deionized water
mol·L-1Suspension；(4) the second source of iron is made into by (0.1-1.0) molL using deionized water-1's
Suspension；(5) carbon source is dissolved using appropriate amount of deionized water, then again mixes each raw material in proportion.
In step s 11, each raw material is emulsified into mixing in proportion and obtains precursor pulp, preferably described breast
The condition for changing mixing includes：It is preferred that the condition of the emulsification mixing includes：It is in rotating speed
2000-3000rpm, temperature is mixed under the conditions of 25-35 DEG C, each raw material to be mixed or being added successively simultaneously
Close, incorporation time is after the charging that (once fed while mixing and calculating, emulsification mixing is once) every time
30-120min。
In a kind of relative specific embodiment of the invention, above-mentioned steps S11 includes：By what is prepared
Slowly be drained to containing the second phosphorus source solution prepare containing the second lithium source solution in the middle of, while open mulser
Emulsified, add the suspension containing the second manganese source for preparing to continue to emulsify after emulsification (30-60) min
(30-60) min, is then slowly added to the scattered suspension containing the second source of iron and continues to emulsify
(30-120) min, obtains (nano level) slurry, adds glucose solution to continue to emulsify (30-60)
Min, obtains (nano level) precursor pulp.
Preferably, the emulsification treatment process is to carry out in the presence of an inert gas.In the present invention can be with
The inert gas for using including but not limited to N2Or Ar.Carrying out emulsification treatment in the presence of an inert gas has
It is oxidized beneficial to raw material are avoided.
In step s 12, the condition of spray drying can for inlet temperature between 280-400 DEG C, go out
Material mouth temperature control is between 100-130 DEG C.Wherein, spray drying is to do carrier gas to preceding with inert gas
Somaplasm material is driven to be spray-dried.Have as carrier gas using inert gas and kept away in the middle of spray-drying process
Exempt from oxidized effect.The inert gas that can be used in the present invention including but not limited to N2Or Ar.
In step s 12, do not have particular/special requirement, Ke Yican for the temperature and time of sintering processes
According to the process conditions that this area routinely uses.The temperature of such as sintering processes is at 550-850 DEG C of sintering
The time of reason is 1-10h.It is 600-750 DEG C in the temperature of preferably sintering processes of the invention, preferably sinters
The time for the treatment of is 2-6h.By sintering temperature and sintering time control within the range, synthesis is conducive to
The content of Magnetic Materials between 900-1150 weight ppm with LiMnxFe1-xPO4The activity of/C-structure
Component.Preferably, sintering is to carry out under an inert atmosphere, the indifferent gas that can be used in the present invention
Body includes but is not limited to N2Or Ar.
In the preparation method of positive electrode active materials provided by the present invention, for the second lithium source, the second iron
Source, manganese source, the selection of the second phosphorus source and second carbon source do not have particular/special requirement, are referred to this area
Conventional selection.The second lithium source that can be used in the present invention including but not limited to lithium hydroxide, carbon
One or more of sour lithium, lithium acetate and lithium acetate；The second source of iron that can be used is included but is not limited to
One or more in ferric phosphate, ferrous oxalate, ferrous acetate and ferrous carbonate；The manganese that can be used
Source includes but is not limited to the one kind or many in manganese phosphate, oxalic acid Asia manganese, acetic acid Asia manganese and carbonic acid Asia manganese
Kind；The second phosphorus source that can be used including but not limited to phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate,
One or more in sodium phosphate, disodium-hydrogen and sodium dihydrogen phosphate；The second carbon source that can be used
One or more including but not limited in glucose, fructose and sucrose.
In the preparation method of positive electrode active materials provided by the present invention, S2 is comprised the following steps：S21、
Described there will be LiMnxFe1-xPO4The active component of/C-structure and first lithium being dissolved in solvent
The mixing of source, first source of iron, first phosphorus source and first carbon source, obtains mixed slurry；
Under S22, hydrothermal synthesizing condition, described with LiMnxFe1-xPO4The active component surface of/C-structure
The LiFePO4 compound-material layer that outer surface coats carbon-coating is formed, positive electrode active materials forerunner is formed
Body；S23, by the positive electrode active materials presoma filtration washing after, through dried process obtain it is described just
Pole active material.Wherein：
In the step s 21, with LiMnxFe1-xPO4The active component of/C-structure is in terms of phosphorus with described
One phosphorus source with the mol ratio that phosphorus is counted be 1：(0.05-0.3), preferably 1:(0.1-0.2)；And described
One phosphorus source in terms of phosphorus, first source of iron in terms of iron, first lithium source with the mol ratio that lithium is counted be 1：
1：(0.9-1.1).The consumption of the first carbon source is that the content of carbon in final products is prepared phosphorus
The 1.5wt%-3wt% of sour ferromanganese lithium class material weight.
In S21, the step of carrying out emulsification treatment after each raw material is mixed is additionally included in, it is preferably described
The condition of emulsification treatment includes：Rotating speed is 2000-3000rpm, and the time is 30-60min, and temperature is
25-35℃.Preferably, the emulsification treatment process is to carry out in the presence of an inert gas.In the present invention
The inert gas that can be used including but not limited to N2Or Ar.
In a kind of relative specific embodiment of the invention, above-mentioned steps S21 includes：(1) will
In 1-100 weight portion steps S1 prepare with LiMnxFe1-xPO4The active component of/C-structure is dissolved in
In the middle of (0.1-1) L deionized waters, lasting stirring；(2) the first source of iron is made into using deionized water
(0.1-0.2)mo·L-1Solution；(3) the first phosphorus source is made into by (0.1-0.2) molL using deionized water-1
Solution；(4) the first lithium source is made into by (0.1-0.7) molL using deionized water-1Solution；(5)
First carbon source is dissolved in the middle of deionized water；(6) under inert atmosphere protection, first for having configured
Lithium source, the first source of iron, the solution of the first phosphorus source are pumped into the speed of 50-200mL/min and prepared simultaneously
It is good with LiMnxFe1-xPO4In the middle of the active component slurry of/C-structure, addition contains the first carbon source
Solution obtains mixed slurry.
In step S22, hydrothermal synthesizing condition is, at 150-300 DEG C, at preferably 150-200 DEG C, to continue
Reaction 1-10h, preferably 2-6h.Hydrothermal synthesizing condition is limited within the above range, is conducive to obtaining magnetic
Of the present invention positive electrode active materials of the content of property thing in the range of 700-850 weight ppm.
In step S23, the temperature of dried process is 200-500 DEG C of drying.Stabilization will be dried to be limited to
Should in the range of be conducive to preventing drying slurry and be oxidized.
In the preparation method of positive electrode active materials provided by the present invention, for the first lithium source, the first iron
Source, the selection of the first phosphorus source and the first carbon source do not have particular/special requirement, as long as can dissolve in a solvent
, specific raw material is referred to the conventional selection of this area.First for can using in the present invention
Lithium source includes but is not limited to one or more of lithium hydroxide, lithium acetate and lithium acetate；Can use
First source of iron includes but is not limited to one or more in ferrous sulfate, frerrous chloride and ferrous nitrate；
The first phosphorus source that can be used including but not limited to phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid
One or more in sodium, disodium-hydrogen and sodium dihydrogen phosphate；The first carbon source that can be used includes
But it is not limited to one or more in glucose, fructose and sucrose.
According to the third aspect of the present invention, a kind of positive electrode active materials are additionally provided, the positive-active
Material is prepared from by above-mentioned preparation method of the invention.This positive electrode active materials, with nucleocapsid knot
Structure, wherein, core portion is with LiMnxFe1-xPO4The active component of/C-structure, 0 ＜ x ＜ 1；Shell bag
The surface in the core portion is overlayed on, is the LiFePO4 compound-material layer that outer surface coats carbon-coating.
Preferably, the content of Magnetic Materials is 700-850 weight ppm in the positive electrode active materials.
Preferably, it is described with LiMnxFe1-xPO4The content of Magnetic Materials is in the active component of/C-structure
900-1150 weight ppm.
Preferably, it is described with LiMnxFe1-xPO4The particle diameter D of the active component of/C-structure50For
100-500nm；The radial thickness of the LiFePO4 compound-material layer of outer surface cladding carbon-coating is
5-25nm。
Preferably, it is described with LiMnxFe1-xPO4In the active component of/C-structure, 0.5≤x ＜ 1,
It is preferably based on LiMnxFe1-xPO4The gross weight of the active component of/C-structure, the tool
There is LiMnxFe1-xPO4Carbon content is 1.5-3wt% in the active component of/C-structure.
Preferably, phosphorus, iron, lithium rub in the LiFePO4 compound-material layer of outer surface cladding carbon-coating
You are than being 1.0：1.0：(0.9-1.1).
It is preferably based on the gross weight of the LiFePO4 compound-material layer of outer surface cladding carbon-coating, institute
Carbon content is 1.5-3wt% in stating the LiFePO4 compound-material layer of outer surface cladding carbon-coating.
Preferably, there is LiMn in the positive electrode active materialsxFe1-xPO4The active component of/C-structure with
The LiFePO4 compound-material layer of phosphorus meter and outer surface cladding carbon-coating with the mol ratio that phosphorus is counted be 1：
(0.05-0.3), preferably 1：(0.1-0.2).
According to the fourth aspect of the present invention, additionally provide a kind of cell size, the cell size be by
Above-mentioned positive electrode active materials configure the paste compound that the solid content to be formed is 10-70wt%.
Also include binding agent and conductive agent in the cell size composition.The wherein original of binding agent and conductive agent
Material and consumption are referred to this area conventional selection, and such as binding agent can be Kynoar, conductive
Agent can be acetylene black, iron manganese phosphate for lithium class material (positive electrode active materials) and conductive agent and binding agent
Weight ratio is 80:10:10.The solvent that can be used in above-mentioned cell size composition is included but is not limited to
One or more in water, ethanol and methyl alcohol.The positive pole includes collector and is arranged on the collector
Anode active material layer, the anode active material layer include iron manganese phosphate for lithium class material of the present invention.
Preferably, above-mentioned collector is referred to metal material commonly used in the art, for example including but not
It is limited to platinum (Pt), palladium (Pd), aluminium (Al) paper tinsel etc..
According to the sixth aspect of the invention, a kind of lithium battery is additionally provided, the lithium battery interior is equipped with
Positive pole, the positive pole includes (being) above-mentioned positive pole.By using above-mentioned positive electrode active materials of the invention
Cell size is prepared from positive pole, the full electricity state high temperature storages of lithium battery 4.3V provided by the present invention it
Afterwards, stain quantity is less than 10/cm on negative material surface2.Process is being used so as to improve battery
In, the easy self discharge of negative material, the not good problem of cycle performance, and improve the use longevity of battery
Life.
Below with reference to specific embodiment and comparative example further illustrate positive electrode active materials of the present invention and its
Preparation method and cell size and lithium battery, and its advantage.
Involved test event and method of testing are as follows in following examples and comparative example：
The content of Magnetic Materials：Tested using JSII-G1 Magnetic Materials analyzers, test condition is：Take
10g samples are put into direct measurement in measuring cylinder；
Particle diameter D50：Tested using winner 2000zd type particle size analyzers, test condition is：Claim
Take 0.1g powder and be put into ultrasonic disperse 10min in 10ml beakers；
Shell thickness：Tested using high magnification transmission electron microscope, test condition is：Intensity
300keV；Electronic Speculum multiplication factor：100K；Sweep speed：2nm/s.
The test condition of XPS collection of illustrative plates includes：
Analyzed area：The circle that about 800 μm of diameter, information depth：About 10nm；
Atom number percentage Monitoring lower-cut：0.1%；
Test environment：Temperature：23.6 DEG C, relative humidity：50%, vacuum：5.0x10-8Torr。
Voltage：15kV, electric current：23mA, power：350W；
X-ray scanning angle：45.0゜.
Embodiment 1-6
For illustrating that core portion is with LiMn0.5Fe0.5PO4Active component (the content of Magnetic Materials of/C-structure
Be 920 weight ppm) positive electrode active materials and preparation method thereof.
Embodiment 1
(1) with LiMn0.5Fe0.5PO4The preparation of the active component (core portion) of/C-structure.
By 57.7gH3PO4、42.1g LiOH·H2O is dissolved separately in the middle of deionized water by mechanical agitation
It is made into 0.5molL-1H3PO4And 1.0molL-1LiOH·H2O solution, by 57.5g carbonic acid Asia manganese,
75.5g ferric phosphates disperse to be made into 0.5molL in deionized water respectively-1Suspension, by 18.66g Portugals
Grape sugar is dissolved in the middle of deionized water；The phosphoric acid solution that will be prepared slowly is drained to 100mL/min speed
In the middle of the lithium hydroxide solution for preparing, while unlatching mulser is emulsified, and (emulsification condition includes：Rotating speed
It is 2500rpm, temperature is 30 DEG C), add the carbonic acid Asia manganese suspension for preparing to continue breast after emulsification 0.5h
Change 0.5h, be then slowly added to scattered ferric phosphate suspension and continue to emulsify 1.0h, add glucose
Solution continues to emulsify 0.5h, obtains precursor pulp；Precursor pulp is spray-dried and (is sprayed dry
Dry condition includes：, at 300 DEG C, discharging opening temperature control is at 120 DEG C for inlet temperature), will be dried
Powder carries out 700 DEG C of sintering, sinters 10h；Particle diameter D is obtained after natural cooling50It is having for 200nm
LiMn0.5Fe0.5PO4The active component of/C-structure.
Microcell power spectrum is swept by high magnification transmission electron microscope line it can be seen that the active component surface is formed with bag
Coating, through by x-ray photoelectron (abbreviation XPS) detect the active component it is surface coated be carbon
Layer, and detect that the internal material of the active component is examined by x-ray photoelectron (abbreviation XPS)
Survey and understand, the inside of active component includes element phosphor, iron, manganese, lithium and oxygen, be computed understanding：Phosphorus,
Iron, manganese, lithium mol ratio are approximately equal to 1：0.5：0.5:1, it can be seen that, above-mentioned active component has
LiMn0.5Fe0.5PO4/ C-structure；And should have LiMn after testing0.5Fe0.5PO4The core portion material of/C-structure
The content of middle Magnetic Materials is 920 weight ppm.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating
By 158.0g above steps obtain with LiMn0.5Fe0.5PO4The active component of/C-structure is made into
1.0mol·L-1Suspension, lasting stirring；By 27.8g FeSO4.7H2O、11.5g H3PO4(purity
It is 85wt%) it is dissolved in deionized water and is made into 0.1molL-1Solution；12.6gLiOH.H2O be dissolved in from
Sub- water is made into 0.3molL-1Solution, 1.09g glucose is dissolved in the middle of deionized water, is protected in nitrogen atmosphere
By ferrous sulfate, the mixed solution of phosphoric acid and lithium hydroxide solution simultaneously with 30mlmin under shield-1Slowly
Pump into prepared with LiMn0.5Fe0.5PO4In the middle of the active component slurry of/C-structure, addition has been matched somebody with somebody
Good glucose solution, while unlatching mulser is emulsified, and (emulsification condition includes：Rotating speed is 2500rpm,
Time is 45min, and temperature is 30 DEG C), the mixed solution after emulsification is warming up to 180 DEG C, continue anti-
Temperature fall after 4h is answered, is washed 3 times using the filter-cloth filtering of deionized water, 1500 mesh, 300 DEG C of drying,
It is the target product of 0.5nm to obtain shell thickness.
Microcell power spectrum is swept by high magnification transmission electron microscope line it can be seen that the target product includes from inside to outside
Four layers, the second layer wherein from inside to outside and the are detected through by x-ray photoelectron (abbreviation XPS)
Four layers are carbon-coating, and detect the material between two carbon-coatings by x-ray photoelectron (abbreviation XPS)
The bed of material includes phosphorus, iron, lithium and oxygen, is computed understanding, wherein phosphorus, iron, lithium mol ratio are approximately equal to 1：
1：1, it can be seen that, above-mentioned target product is with LiMn0.5Fe0.5PO4The active component of/C-structure
Surface forms the LiFePO4 compound-material layer that outer surface coats carbon-coating；Scanned Electronic Speculum spectrogram can be with
See that the target product shell layer surface is uniform, smooth, and magnetic in the iron manganese phosphate for lithium class active component after testing
Property thing content be 820 weight ppm.
Embodiment 2
(1) with LiMn0.5Fe0.5PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 1.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Embodiment 1, difference is：
FeSO4·7H2The consumption of O is 55.6g；H3PO4The consumption of (purity is 85wt%) is 23.0g；
LiOH·H2The consumption of O is 25.2g；The consumption of glucose is 3.0g.The final shell thickness that obtains is 1.0nm
Target product, after testing in above-mentioned target product Magnetic Materials content be 780 weight ppm.
Embodiment 3
(1) with LiMn0.5Fe0.5PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 1.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Embodiment 1, difference is：
FeSO4·7H2The consumption of O is 13.9g；H3PO4The consumption of (purity is 85wt%) is 5.76g；
LiOH·H2The consumption of O is 6.3g；The consumption of glucose is 0.55g.Finally obtaining shell thickness is
The target product of 0.24nm, the content of Magnetic Materials is 850 weight ppm in above-mentioned target product after testing.
Embodiment 4
(1) with LiMn0.5Fe0.5PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 1.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Embodiment 1, difference is：
FeSO4·7H2The consumption of O is 83.4g；H3PO4The consumption of (purity is 85wt%) is 34.5g；
LiOH·H2The consumption of O is 37.8g；The consumption of glucose is 3.3g.The final shell thickness that obtains is 1.5nm
Target product, after testing in prepared target product Magnetic Materials content be 750 weight ppm.
Embodiment 5
(1) with LiMn0.5Fe0.5PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 1.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Method in embodiment 1, difference is, without emulsification treatment after each raw material is mixed, directly to carry out hydro-thermal
Synthesis is processed, and the content of Magnetic Materials is 860 weight ppm in prepared target product after testing.
Embodiment 6
(1) with LiMn0.5Fe0.5PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 1.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Method in embodiment 1, difference is that drying temperature is 500 DEG C, after testing prepared target product
The content of middle Magnetic Materials is 850 weight ppm.
Embodiment 7-9
For illustrating that core portion is with LiMn0.7Fe0.3PO4The positive electrode active materials of the active component of/C-structure
And preparation method thereof.
Embodiment 7
(1) with LiMn0.7Fe0.3PO4The preparation of the active component (core portion) of/C-structure
By 80.8gH3PO4、42.1g LiOH·H2O is dissolved separately in the middle of deionized water by mechanical agitation
It is made into 0.7molL-1H3PO4And 1.0molL-1LiOH·H2O solution, by 73.5g carbonic acid Asia manganese,
56.1g ferric phosphates disperse to be made into 0.7molL in deionized water respectively-1And 0.3molL-1Suspension,
8.2g glucose is dissolved in the middle of deionized water；The phosphoric acid solution that will be prepared is with 100mL/min speed
Slowly it is drained in the middle of the lithium hydroxide solution for preparing, while opening mulser is emulsified (emulsification condition
Including：Rotating speed 3000rpm, temperature is 35 DEG C), add the carbonic acid Asia manganese for preparing to suspend after emulsification 0.5h
Liquid continues to emulsify 0.5h, is then slowly added to scattered ferric phosphate suspension and continues to emulsify 1.0h, plus
Enter glucose solution to continue to emulsify 0.5h, obtain precursor pulp；Precursor pulp is spray-dried
(condition of spray drying be inlet temperature at 280 DEG C, discharging opening temperature control is at 130 DEG C), by drying
Powder afterwards carries out 750 DEG C of sintering 10h, and particle diameter D is obtained after natural cooling50It is having for 21nm
LiMn0.7Fe0.3PO4The active component of/C-structure, should have LiMn after testing0.7Fe0.3PO4/ C-structure
The content of Magnetic Materials is 940 weight ppm in active component.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：
By 158.0g above steps obtain with LiMn0.7Fe0.3PO4The active component of/C-structure is made into
1.0mol·L-1Suspension, lasting stirring；13.9g FeSO4·7H2O、5.76g H3PO4(purity is
85wt%) it is dissolved in deionized water and is made into 0.05molL-1Solution；6.3gLiOH·H2O is dissolved in deionized water
It is made into 0.15molL-1Solution, 1.5g glucose is dissolved in the middle of deionized water, under nitrogen atmosphere protection
By ferrous sulfate, the mixed solution of phosphoric acid and lithium hydroxide solution simultaneously with 30mlmin-1Slowly pump into
Prepared with LiMn0.7Fe0.3PO4In the middle of the active component slurry of/C-structure, what addition had been prepared
Glucose solution, while unlatching mulser is emulsified, and (emulsification condition includes：Rotating speed is 3000rpm,
Time is 30min, and temperature is 35 DEG C), the mixed solution after emulsification is warming up to 200 DEG C, continue anti-
Answer Temperature fall after 2h, filtration washing 3 times, 300 DEG C of drying, it is 0.25nm's to obtain shell thickness
Target product, the content of Magnetic Materials is 830 weight ppm in above-mentioned target product after testing.
Embodiment 8
(1) with LiMn0.7Fe0.3PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 7.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Method in embodiment 7, difference is that drying temperature is 500 DEG C, after testing prepared target product
The content of middle Magnetic Materials is 840 weight ppm.
Embodiment 9
(1) with LiMn0.7Fe0.3PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 7.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Embodiment 7, difference is：
FeSO4·7H2The consumption of O is 27.8g；H3PO4Consumption be 11.5g；LiOH·H2The consumption of O
It is 12.6g；The consumption of glucose is 1.5g.The final shell thickness that obtains is the target product of 0.5nm,
The content of Magnetic Materials is 790 weight ppm in prepared target product after testing.
Embodiment 10-11
For illustrating that core portion is with LiMn0.9Fe0.1PO4Active component (the content of Magnetic Materials of/C-structure
950 weight ppm) positive electrode active materials and preparation method thereof.
Embodiment 10
(1) with LiMn0.9Fe0.1PO4The preparation of the active component (core portion) of/C-structure.
By 103.8gH3PO4、42.1g LiOH·H2O is dissolved separately in deionized water and works as by mechanical agitation
In be made into 0.9molL-1H3PO4And 1.0molL-1LiOH·H2O solution, by 103.5g carbonic acid Asia manganese,
15.1g ferric phosphates disperse to be made into 0.9molL in deionized water respectively-1And 0.1molL-1Suspension,
2.7g glucose is dissolved in the middle of deionized water；The phosphoric acid solution that will be prepared is with 100mL/min speed
Slowly it is drained in the middle of the lithium hydroxide solution for preparing, while opening mulser is emulsified (emulsification condition
It is 2000rpm including rotating speed, temperature is 25 DEG C), add the carbonic acid Asia manganese for preparing to suspend after emulsification 0.5h
Liquid continues to emulsify 0.5h, is then slowly added to scattered ferric phosphate suspension and continues to emulsify 1.0h, plus
Enter glucose solution to continue to emulsify 0.5h, obtain precursor pulp；Precursor pulp is spray-dried,
Dried powder is carried out into 600 DEG C of sintering 10h, particle diameter having for 210nm is obtained after natural cooling
LiMn0.9Fe0.1PO4The active component of/C-structure, should have LiMn after testing0.9Fe0.1PO4/ C-structure
The content of Magnetic Materials is 950 weight ppm in active component.
By 158.0g above steps obtain with Li Mn0.9Fe0.1PO4The active component of/C-structure is made into
1.0mol·L-1Suspension, lasting stirring；13.9g FeSO4·7H2O、5.76g H3PO4(purity is
85wt%) it is dissolved in deionized water and is made into 0.05molL-1Solution；6.3gLiOH·H2O is dissolved in deionized water
It is made into 0.15molL-1Solution, 0.55g glucose is dissolved in the middle of deionized water, in nitrogen atmosphere protection
It is lower by ferrous sulfate, the mixed solution of phosphoric acid and lithium hydroxide solution simultaneously with 30mlmin-1Slow pump
Enter prepared with Li Mn0.9Fe0.1PO4In the middle of the active component of/C-structure, the Portugal that addition has been prepared
Grape sugar juice, while unlatching mulser is emulsified, and (emulsification condition includes：Rotating speed is 2000rpm, when
Between be 60min, temperature be 25 DEG C), the mixed solution after emulsification is warming up to 150 DEG C, sustained response
Temperature fall after 6h, filtration washing 3 times, 300 DEG C of drying, it is the target of 0.26nm to obtain shell thickness
Product, the content of Magnetic Materials is 840 weight ppm in prepared target product after testing.
Embodiment 11
(1) with LiMn0.9Fe0.1PO4The preparation of the active component (core portion) of/C-structure：With implementation
Example 10.
(2) preparation of the LiFePO4 compound-material layer (shell) of outer surface cladding carbon-coating：Reference
Method in embodiment 5, difference is that drying temperature is 500 DEG C, after testing prepared target product
The content of middle Magnetic Materials is 850 weight ppm.
Comparative example 1 and 2
For to positive electrode active materials of the present invention and preparation method thereof as directed.
Comparative example 1
By 57.7gH3PO4、42.1g LiOH·H2O is dissolved separately in the middle of deionized water by mechanical agitation
It is made into 0.5molL-1H3PO4And 1.0molL-1LiOH·H2O solution, by 57.5g carbonic acid Asia manganese,
75.5g ferric phosphates disperse to be made into 0.5molL in deionized water respectively-1Suspension, by 18.66g Portugals
Grape sugar is dissolved in the middle of deionized water；The phosphoric acid solution that will be prepared slowly is drained to 100mL/min speed
In the middle of the lithium hydroxide solution for preparing, while unlatching mulser is emulsified, and (emulsification condition is inlet temperature
Between 300 DEG C, discharging opening temperature control is between 120 DEG C), add the carbonic acid for preparing after emulsification 0.5h
Sub- manganese suspension continues to emulsify 0.5h, is then slowly added to scattered ferric phosphate suspension and continues to emulsify
1.0h, obtains precursor pulp, adds glucose solution to continue to emulsify 0.5h；Slurry is carried out into spraying dry
It is dry, dried powder is carried out into 700 DEG C of sintering, obtained with LiMn after natural cooling0.5Fe0.5PO4/C
The active component of structure.There should be LiMn after testing0.5Fe0.5PO4Magnetic Materials in the active component of/C-structure
Content be 920 weight ppm.
Comparative example 2
0.03mol manganese carbonates, 0.03mol diammonium hydrogen phosphates, 0.015mol are weighed according to equimolar ratio
Lithium carbonate, in addition corundum ball grinder, and adds ethanol in proper amount, the ball milling 1h in oscillatory type ball mill,
Be obtained the second precursors, by second precursors in Ar air-flows in 600 DEG C of temperature conditionss
Lower heat treatment 5 hours, is obtained LiMnPO4Material, weighs 1.5g LiMnPO4With 0.91g phosphoric acid
Iron (FePO4·4H2O), 0.186g lithium hydroxides (LiOHH2O), 0.5g glucose mixing, and add
5mL ethanol ball milling is obtained the first precursors.By first precursors in Ar air-flows
600 DEG C are heat-treated 10 hours, and LiFePO4 cladding iron manganese phosphate lithium composite is prepared using this technology
Material, the wherein content of Magnetic Materials are 1100 weight ppm.
Test：
(1) preparation of positive pole：Respectively with the iron manganese phosphate prepared by embodiment 1-11 and comparative example 1-2
Lithium class material is positive-active raw material, and the positive electrode active materials, acetylene black, Kynoar (are purchased from
Dongguan City Qing Feng plastic materials Co., Ltd, the trade mark is FR900) by weight it is 80:10:10 are dissolved in
It is the cell size of 50wt% that solid content is formed in 1-METHYLPYRROLIDONE, and is obtained after stirring
Slurry coating on the aluminium foil that thickness is 25 μm, and at 110 DEG C ± 5 DEG C toast, forming thickness is
20 μm of material layer, obtains positive electrode S1-S11 and DS1-DS2.
(2) preparation of lithium ion monolithic battery：Respectively application positive pole S1-S11 and D1-D2 make lithium from
Sub- monolithic battery, in made battery negative material be native graphite, diaphragm material be commercially available from
The Celgard PE films of Celgard companies, electrolyte is 1mol/LLiPF6/ (EC+DMC) is (wherein
LiPF6 is lithium hexafluoro phosphate, and EC is ethylene carbonate, and DMC is dimethyl carbonate, EC and DMC
Volume ratio be 1:1)), made battery is designated as T1-T11 and DT1-DT2 respectively.
(3) test event and method
Stain quantity on negative material：The battery S1-S11 and D1-D2 of foregoing preparation are respectively charged in
The full electricity states of 4.3V, visually observe the stain quantity of GND after storage under the conditions of 60 DEG C of battery 7 days.
High temperature cyclic performance：In 45 DEG C of baking ovens, by the battery S1-S11 and D1-D2 of foregoing preparation point
Constant current constant voltage is not carried out with the electric current of 1C to circulate 3000 times, the discharge capacity of the 3000th time with the 1st time
The ratio of discharge capacity be 3000 high temperature circulation capability retentions of the battery.
Battery capacity conservation rate (life test) after being stored 4 days under the conditions of 85 DEG C：First by battery in 0.1C
Discharge and recharge one week (7 days) under electric current, record discharge capacity C0；It is again that battery is fully charged under 0.1C
After being stored 4 days under the conditions of 85 DEG C afterwards, after taking out battery cooling, discharge into by voltage 2.5V, note
Record residual capacity C1,7 days capability retentions of battery 85 DEG C are (C0/C1) * 100%.
(4) test result：As shown in table 1.
Table 1.
| Test event | T1 | T2 | T3 | T4 | T5 | T6 | T7 |
| Stain quantity (individual/cm2) | 4 | 2 | 6 | 2 | 10 | 3 | 3 |
| Cycle performance (%) | 98.6 | 97.2 | 92.3 | 91.5 | 90.7 | 98.6 | 97.6 |
| 85 DEG C of 4 days conservation rates (%) | 96.4 | 96.8 | 94.4 | 93.2 | 91.2 | 97.4 | 97.2 |
| Test event | T8 | T9 | T10 | T11 | DT1 | DT2 | |
| Stain quantity (individual/cm2) | 4 | 2 | 5 | 4 | 21 | 24 | |
| Cycle performance (%) | 98.0 | 98.2 | 98.3 | 99.0 | 75.3 | 70.8 | |
| 85 DEG C of 4 days conservation rates (%) | 97.3 | 97.5 | 97.8 | 96.2 | 80.6 | 77.2 |
Be could be aware that by data in embodiment 1 to 11 and table 1, compared with documents 1 and 2,
Positive electrode active materials prepared by according to embodiments of the present invention 1 to 11, by having
LiMnxFe1-xPO4The active component outside of/C-structure forms the LiFePO4 chemical combination that outer surface coats carbon-coating
Thing material layer, can be effectively reduced the content of Magnetic Materials in prepared positive electrode active materials.
In positive pole prepared by the positive electrode active materials provided using embodiment 1 to 11, electricity is made
Stain quantity, the energy of GND after being stored 7 days under the conditions of 60 DEG C can be substantially reduced after the T1-T11 of pond
Enough significantly improve 45 DEG C, battery capacity conservation rate and 85 DEG C can be significantly improved after 3000 circulations
Under the conditions of storage 4 days after battery capacity conservation rate, and then be conducive to extend battery service life.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in implementation method, in range of the technology design of the invention, can be to skill of the invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid not
Necessary repetition, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as
, without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention for it.
Claims (21)
1. a kind of positive electrode active materials, it is characterised in that the positive electrode active materials have core shell structure,
Wherein, core portion is with LiMnxFe1-xPO4The active component of/C-structure, 0 ＜ x ＜ 1；Shell is coated on
The surface in the core portion, is the LiFePO4 compound-material layer of outer surface cladding carbon-coating.
2. positive electrode active materials according to claim 1, wherein, in the positive electrode active materials
The content of Magnetic Materials is 700-850 weight ppm.
3. positive electrode active materials according to claim 1, wherein, it is described to have
LiMnxFe1-xPO4The content of Magnetic Materials is 900-1150 weight ppm in the active component of/C-structure.
4. positive electrode active materials according to claim 1, wherein, it is described to have
LiMnxFe1-xPO4The particle diameter D of the active component of/C-structure50It is 100-500nm；The outer surface cladding
The radial thickness of the LiFePO4 compound-material layer of carbon-coating is 5-25nm.
5. positive electrode active materials as claimed in any of claims 1 to 4, wherein, it is described
With LiMnxFe1-xPO4In the active component of/C-structure, 0.5≤x ＜ 1,
It is preferably based on LiMnxFe1-xPO4The gross weight of the active component of/C-structure, the tool
There is LiMnxFe1-xPO4Carbon content is 1.5-3wt% in the active component of/C-structure.
6. positive electrode active materials as claimed in any of claims 1 to 4, wherein, appearance
It is 1 that bread covers phosphorus in the LiFePO4 compound-material layer of carbon-coating, iron, the mol ratio of lithium：1：
(0.9-1.1),
It is preferably based on the gross weight of the LiFePO4 compound-material layer of outer surface cladding carbon-coating, institute
Carbon content is 1.5-3wt% in stating the LiFePO4 compound-material layer of outer surface cladding carbon-coating.
7. positive electrode active materials according to claim 6, wherein, in the positive electrode active materials
With LiMnxFe1-xPO4The active component of/C-structure coats the LiFePO4 of carbon-coating in terms of phosphorus with outer surface
Compound-material layer with the mol ratio that phosphorus is counted be 1：(0.05-0.3), preferably 1：(0.1-0.2).
8. a kind of preparation method of positive electrode active materials, it is characterised in that the preparation method include with
Lower step：
S1, offer have LiMnxFe1-xPO4The active component of/C-structure, 0 ＜ x ＜ 1；
S2, under hydrothermal synthesizing condition, described will have LiMnxFe1-xPO4The active component of/C-structure
Mix in a solvent with the first lithium source, the first source of iron, the first phosphorus source and the first carbon source and contact, form described
Positive electrode active materials.
9. preparation method according to claim 8, wherein, containing for Magnetic Materials is provided in the S1
It is the active component of 900-1150 weight ppm to measure, it is preferable that the particle diameter D of the active component50
It is 100-500nm, more preferably in active component, 0.5≤x ＜ 1, carbon content in particularly preferred active component
It is 1.5-3wt%.
10. preparation method according to claim 8, wherein, the S1 is comprised the following steps：
S11, the second lithium source, the second source of iron, manganese source, the second phosphorus source and second carbon source are mixed in proportion
Close, obtain precursor pulp；
S12, the precursor pulp is sequentially passed through spray drying, sintering formed described in have
LiMnxFe1-xPO4The active component of/C-structure.
11. preparation methods according to claim 9, wherein, in the S11 by each raw material press than
Example emulsification mixing obtains precursor pulp, and the condition of preferably described emulsification mixing includes：It is in rotating speed
2000-3000rpm, temperature is mixed under the conditions of 25-35 DEG C, each raw material to be mixed or being added successively simultaneously
Close, incorporation time is 30-120min after charging every time.
12. preparation methods according to claim 9, wherein, the temperature of sintering processes in the S12
It is 550-850 DEG C to spend, preferably 600-750 DEG C, and the time of sintering processes is 1-10h, preferably
2-6h。
13. preparation methods according to claim 8, wherein, the S2 is comprised the following steps：
S21, general are described with LiMnxFe1-xPO4The active component of/C-structure be dissolved in solvent
The mixing of first lithium source, first source of iron, first phosphorus source and first carbon source, obtains
Mixed slurry；
Under S22, hydrothermal synthesizing condition, described with LiMnxFe1-xPO4The active component of/C-structure
Surface forms the LiFePO4 compound-material layer that outer surface coats carbon-coating, before forming positive electrode active materials
Drive body；
S23, by the positive electrode active materials presoma filtration washing after, through dried process obtain it is described just
Pole active material.
14. preparation methods according to claim 13, wherein, have in the S21
LiMnxFe1-xPO4Mol ratio of the active component of/C-structure in terms of phosphorus with first phosphorus source in terms of phosphorus be
1：(0.05-0.3), preferably 1:(0.1-0.2)；And first phosphorus source is in terms of phosphorus, described first
Source of iron in terms of iron, first lithium source with the mol ratio that lithium is counted be 1：1：(0.9-1.1), the first carbon source
Consumption for the content of carbon in final products be prepared iron manganese phosphate for lithium class material weight
1.5wt%-3wt%.
15. preparation methods according to claim 13, wherein, the S21 is additionally included in will be each
The step of carrying out emulsification treatment after raw material mixing, the condition of preferably described emulsification treatment includes：Rotating speed is
2000-3000rpm, the time is 30-60min, and temperature is 25-35 DEG C.
16. preparation methods according to claim 13, wherein, Hydrothermal Synthesiss bar in the S22
Part be at 150-300 DEG C, at preferably 150-200 DEG C, sustained response 1-10h, preferably 2-6h.
17. preparation methods according to claim 13, wherein, the temperature of the dried process is
200-500 DEG C of drying.
A kind of 18. positive electrode active materials, it is characterised in that the positive electrode active materials by above-mentioned 8 to
Preparation method in 17 described in any one is prepared from.
A kind of 19. cell sizes, the cell size includes positive electrode active materials and solvent, its feature
It is, positive pole of the positive electrode active materials described in any one in claim 1 to 7 and 18
Active material.
A kind of 20. positive poles, the positive pole includes that collector and the positive pole being arranged on the collector are lived
Property material layer, it is characterised in that the anode active material layer include claim 1 to 7 and 18
Positive electrode active materials described in middle any one.
A kind of 21. lithium batteries, the lithium battery interior is equipped with positive pole, wherein, the positive pole includes power
Profit requires the positive pole described in 20.
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