CN106981648A - Composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole - Google Patents
Composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole 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
- H01M4/366—Composites as layered products
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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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- H—ELECTRICITY
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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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- H01M4/02—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
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Abstract
A kind of lithium ion battery the invention provides composite positive pole, its preparation method and comprising the composite positive pole.Lithium manganese phosphate that the composite positive pole of the present invention is adulterated by metal ion Li and coat the conductive carbon layer on its surface and constitute, and metal ions M is evenly distributed on inside lithium manganese phosphate and occupies Li, in M=Na, K, Mg or Al any one or at least two combination.Metal ion mixing reduces the particle size of composite positive pole in the composite of the present invention, shortens Li+Diffusion path, improve Li+Intercalation/deintercalation speed, improve the ionic conductivity of metal ion mixing positive electrode, the introducing of 2 layers of conductive carbon layer improves associativity and electric conductivity, the composite positive pole of the present invention is highly suitable as anode active material of lithium ion battery, and the cycle performance and security performance of obtained lithium ion battery are significantly improved.
Description
Technical field
The invention belongs to electrochemical material technical field, it is related to a kind of composite positive pole, its preparation method and lithium ion
Battery, more particularly to a kind of composite positive pole being made up of the lithium manganese phosphate and conductive carbon of Li doping of metal ion, its system
Preparation Method and the lithium ion battery for including the composite positive pole.
Background technology
National 863 development in Hi-Tech plan is included in from electric automobile, New Energy Sources In China automobile industry is obtained nearly ten years
Quickly development, but the development of New Energy Sources In China automobile power cell has directionality dispute always：LiMn2O4, ternary lithium, phosphorus
Sour iron lithium battle is not calmed down all the time.At present, using safety problem be at this stage new-energy automobile develop key element first of.
New Energy Sources In China automobile is to development, it is necessary to assure safe and reliable, performance stabilization and electrokinetic cell with low cost, wherein,
It is safe and reliable be it is the first, without safety there will be no the future of new-energy automobile industry.The safety issue frequency of ternary lithium electricity
Go out, if broken through without big technology and technique, only in terms of material modification or improve pole piece compaction density and come hoist capacity, meeting
Battery is greatly lowered to cycle performance.Tesla using in ternary lithium electricity preferably to Panasonic's battery, with unavoidable five weeks it
Catch fire for interior three times.If the developing direction of New Energy Sources In China automobile power cell is positioned at development ternary lithium electricity, not only long-term place
In pursuit Japan and Korea S enterprise status, and due to a lack of key technology, technique and equipment, a development bottleneck has been trapped in it.And phosphorus
Sour lithium iron battery absolute predominance electric relative to ternary lithium in security and cycle life, exactly New Energy Sources In China vehicle key
Where key element and needed for development.The stability of ferric phosphate lithium cell at high temperature, up to more than 390 DEG C, it is ensured that in battery
High security, will not because overcharging, temperature it is too high, short-circuit, hit and produces blast or burning, meeting current power lithium battery just
Pole material is for security to requiring.
Pure electric automobile (EV) proposes the requirement for improving energy density to lithium ion battery (LIB).LiMnPO4With phase
For Li/Li+The higher energy density of current potential and 695Wh/kg higher about 4.1V, and lithium manganese phosphate cheaper, into
For new type power anode material for lithium-ion batteries.However, LiMnPO4Its low intrinsic conductivity and ionic conductivity cause Li+Expand
Dissipate speed slow, seriously limit development of the material in dynamic lithium battery field.Using metal ion mixing, particle size nanometer
The means such as change and Surface coating can significantly improve LiMnPO4The electric conductivity of positive electrode, and then improve the electrochemistry of material
Energy.
But, by Li doping vario-property LiMnPO of metal ion4It is compound to be used as high performance positive electrode, need into
One step research.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of composite positive pole, its preparation side
Method and lithium ion battery.The composite positive pole of the present invention can significantly improve Li+Intercalation/deintercalation speed, improve metal
The ionic conductivity of ion doping positive electrode, the active material of lithium ion cell positive is used as using the composite positive pole of the present invention
The obtained lithium ion battery of material has excellent performance, and cycle performance and security performance are significantly improved..
In a first aspect, the present invention provides a kind of composite positive pole, the composite positive pole is mixed for Li by metal ion
Miscellaneous lithium manganese phosphate and the conductive carbon layer on the surface for the lithium manganese phosphate for being coated on the metal ion Li doping are constituted, the gold
Category ion is any one in sodium ion, potassium ion, magnesium ion or aluminium ion or at least two combination.
In the present invention, the metal ion be sodium ion, potassium ion, magnesium ion or aluminium ion in any one when, refer to
The metal ion of single kind adulterates to Li.
In the present invention, the metal ion is at least two combination in sodium ion, potassium ion, magnesium ion or aluminium ion
When, refer to two or more metal ions and Li are adulterated simultaneously, such as：Sodium ion and potassium ion simultaneously to Li doping, magnesium from
Son and sodium ion adulterate to Li simultaneously, and sodium ion, potassium ion and aluminium ion adulterate to Li simultaneously.
In the present invention, metal ion is evenly distributed on the inside of lithium manganese phosphate, and metal ion occupies a part of Li.
In the present invention, the chemical composition of the composite positive pole is Li1-xMxMnPO4/ C, wherein, M=Na, K, Mg or Al
In any one or at least two combination, 0<x<1.
Preferably, the pattern of the composite positive pole be near-spherical or it is spherical in any one or at least two group
Close.
Preferably, the size of the composite positive pole is in 50nm-150nm, for example, 50nm, 55nm, 60nm, 65nm,
70nm, 80nm, 85nm, 90nm, 95nm, 100nm, 110nm, 115nm, 125nm, 130nm, 140nm or 150nm etc..
In the present invention, described " size of composite positive pole refers in 50nm-150nm "：Composite positive pole is in three-dimensional side
Upward length is between 50nm-150nm.
Preferably, in the composite positive pole, the thickness of conductive carbon layer is 4nm-8nm, for example, 4nm, 5nm,
5.5nm, 6nm, 7nm or 8nm etc..
Preferably, counted using the Li ions and the total moles quality of metal ion in composite as 100%, the metal from
Son molal weight percentage composition be 0.1mol.%-40mol.%, for example, 0.2mol.%, 0.5mol.%, 1.0mol.%,
2.0mol.%, 5.0mol.%, 8.0mol.%, 10mol.%, 15mol.%, 20mol.%, 25mol.%, 30mol.%,
35mol.% or 38mol.% etc..
Unless otherwise specified, described " mol.% " refers both to molal weight percentage composition.
Preferably, counted using the gross mass of the composite as 100%, the weight percentage of the conductive carbon layer is
1%-40%, for example, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 20%, 23%, 26%, 28%, 30%,
32.5%th, 35%, 37%, 38.5% or 40% etc..
Preferably, the surface coated conductive carbon layer of the lithium manganese phosphate of the metal ion Li doping is 2 layers of conductive carbon
Layer.
Preferably, 2 layers of conductive carbon layer for being coated on the surface of the lithium manganese phosphate of Li doping of metal ion are divided from inside to outside
Be not by polyethylene glycol and carbon source through calcining the conductive carbon layer being transformed, the carbon source preferably include ascorbic acid, glucose,
In sucrose, citric acid, glycolic, butanedioic acid, PVA, ethylene glycol any one or at least two combination.
Second aspect, the present invention provides the preparation method of composite positive pole as described in relation to the first aspect, methods described bag
Include following steps：
(1) prepare the lithium phosphate of the doping of metal ion Li, the metal ion be sodium ion, potassium ion, magnesium ion or
In aluminium ion any one or at least two combination；
(2) lithium phosphate by the Li doping of manganese sulfate and metal ion is added in the mixed solution of polyethylene glycol and water,
Obtain mixed material；
(3) mixed material is transferred in reactor, then the reactor for being contained with mixed material is put into homogeneous reactor,
Hydro-thermal reaction is carried out under conditions of homogeneous reactor rotation, the lithium manganese phosphate presoma of Li doping of metal ion, institute is obtained
It is any one in sodium ion, potassium ion, magnesium ion or aluminium ion or at least two combination to state metal ion；
(4) bag carbon processing is carried out to the lithium manganese phosphate presoma of Li doping of metal ion using carbon source, calcining is answered
Positive electrode is closed, lithium manganese phosphate that the composite positive pole is adulterated by metal ion Li and described metal ion Li are coated on
The conductive carbon layer on the surface of the lithium manganese phosphate of doping is constituted, and the metal ion is sodium ion, potassium ion, magnesium ion or aluminium ion
In any one or at least two combination.
In the method for the present invention, step (3) " the lithium manganese phosphate presoma of Li doping of metal ion " and step (4)
The species of metal ion in " lithium manganese phosphate of Li doping of metal ion " is by " metal ion step (1) Suo Shu
What the species of metal ion of the lithium phosphate of Li doping " was determined.
In the method for the present invention, the conductive carbon layer of introducing includes 2 layers altogether, and this 2 layers of conductive carbon layers are introduced by step (2) respectively
Poly- diethanol and step (4) introduce carbon source through calcining be transformed.
In the method for the present invention, the typical case of the lithium phosphate of the Li doping of metal ion of step (1) but non-limiting examples
Have：The lithium phosphate (referred to as sodium phosphate lithium) of Li doping of sodium ion, the lithium phosphate of Li doping of potassium ion (is referred to as potassium phosphate
Lithium), the lithium phosphate (referred to as magnesium phosphate lithium) of Li doping of magnesium ion, the lithium phosphate of Li doping of aluminium ion (is referred to as phosphoric acid
Aluminium lithium), the lithium phosphate (referred to as potassium-sodium phosphates lithium) of sodium ion and the common Li doping of potassium ion, sodium ion and aluminium ion are common
The lithium phosphate (referred to as acidic sodium aluminum phosphate lithium) of Li doping, the lithium phosphate of potassium ion, magnesium ion and aluminium ion co-doped is (referred to as
Potassium phosphate magnalium lithium) etc..
In the lithium phosphate of Li doping of metal ion prepared by step (1) of the present invention, metal ion (M=Na, K, Mg, Al)
Occupy Li.
Preferably, during the pattern of the lithium phosphate of Li doping of the metal ion described in step (1) is spherical or spherical
Any one or at least two combination.
Preferably, the size of the lithium phosphate of the doping of the metal ion described in step (1) Li is in 100nm-500nm, for example
For 100nm, 125nm, 150nm, 160nm, 180nm, 200nm, 210nm, 225nm, 245nm, 260nm, 280nm, 300nm,
325nm, 350nm, 370nm, 380nm, 400nm, 420nm, 440nm, 460nm, 475nm or 500nm etc..
In the present invention, described " size of the lithium phosphate of Li doping of metal ion refers in 100nm-500nm "：Metal ion
Length of the lithium phosphate of Li doping on three-dimensional is between 100nm-500nm.
As the optimal technical scheme of the method for the invention, step (1) phosphorus for preparing Li doping of metal ion
The process of sour lithium is：
In the mixed solution that phosphoric acid solution is added dropwise to lithium hydroxide and metal salt, sediment is obtained, this sediment is
The lithium phosphate of Li doping of metal ion；Wherein, metal salt be sodium salt, sylvite, magnesium salts or aluminium salt in any one or at least
Two kinds of combination.
Preferably, during the lithium phosphate for preparing Li doping of metal ion, the concentration of phosphoric acid solution is 0.5mol/L-
3.0mol/L, for example, 0.6mol/L, 0.7mol/L, 0.8mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L
Or 2.8mol/L etc..
Preferably, during the lithium phosphate for preparing Li doping of metal ion, the mixing of lithium hydroxide and metal salt is molten
The concentration of metal salt in liquid be 0.1-2.0mol/L, for example, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1.2mol/L,
1.5mol/L or 1.8mol/L etc..
Preferably, during the lithium phosphate for preparing Li doping of metal ion, the mixing of lithium hydroxide and metal salt is molten
The concentration of lithium hydroxide in liquid be 1.0mol/L-3.0mol/L, for example, 1.2mol/L, 1.5mol/L, 1.8mol/L,
2.0mol/L, 2.2mol/L, 2.5mol/L or 2.8mol/L etc..
Preferably, during the lithium phosphate for preparing Li doping of metal ion, phosphoric acid solution and lithium hydroxide and metal
The volume ratio of the mixed solution of salt is 1:2~1:5, for example, 1:2、1:2.2、1:2.5、1:2.8、1:3、1:3.2、1:3.5、1:
4、1:4.2、1:4.5 or 1:5 etc..
Preferably, during the lithium phosphate for preparing Li doping of metal ion, the flow rate of the instillation is 1mL/
Min-10mL/min, for example, 1.5mL/min, 2mL/min, 2.5mL/min, 3mL/min, 3.5mL/min, 4mL/min,
4.5mL/min、5mL/min、5.5mL/min、6mL/min、6.5mL/min、7mL/min、7.5mL/min、8mL/min、
8.5mL/min or 9mL/min etc..
Preferably, during the lithium phosphate for preparing Li doping of metal ion, in addition to sediment is washed
Wash, dried and screened the step of, the drying be preferably vacuum drying.
Preferably, the mol ratio of the lithium phosphate of Li doping of step (2) manganese sulfate and metal ion is (0.5-3):
1, for example, 0.8:1、1.2:1、1.5:1、1.8:1、2.0:1、2.5:1 or 2.8:1 etc..
Preferably, the volume ratio of step (2) polyethylene glycol and water is (0.5-5):2, for example, 0.8:2、1.0:2、
1.2:2、1.5:2、1.8:2、2.0:2、2.5:2、3.0:2、3.5:2、3.8:2、4.0:2、4.5:2 or 4.8:2 etc..
Preferably, step (2) described polyethylene glycol is any one in PEG200, PEG400, PEG800 or PEG2000
Or at least two combination, combination typical case but non-limiting examples have：PEG200 and PEG400 combination, PEG200 with
PEG800 combination, PEG200, PEG400 and PEG800 combination, PEG200, PEG400 and PEG2000 combination, PEG200,
PEG400, PEG800 and PEG2000 combination etc..
The polyethylene glycol used in step (2) of the present invention, on the one hand can divide with water collectively as solvent there is provided good
Property is dissipated, on the other hand, the polyethylene glycol that this step is introduced into is converted into conductive carbon layer in subsequent firing steps, lifts leading for material
Electrically, and this layer of conductive carbon layer introducing be also beneficial to improve with step (4) introduce carbon source conversion conductive carbon layer knot
Conjunction property.
Preferably, step (3) described mixed material also needs to be stirred vigorously before being transferred to reactor, described acutely to stir
Finger stir speed (S.S.) is mixed in 200r/min~400r/min stirring, the speed is, for example, 200r/min, 225r/min, 250r/
Min, 280r/min, 300r/min, 320r/min, 360r/min, 370r/min, 385r/min or 400r/min etc..In order to up to
To the stir speed (S.S.) of this scope, the gear of mixing plant can be adjusted, for example agitator ZXF- of the regulation with gear
8-200 gear is to high tap position 10-20 gears.
Preferably, the rotating speed of step (3) the homogeneous reactor rotation is 40r/min-80r/min, for example, 40r/
Min, 50r/min, 60r/min, 65r/min, 70r/min, 75r/min or 80r/min etc..
Preferably, the temperature of step (3) described hydro-thermal reaction be 140 DEG C -200 DEG C, for example, 145 DEG C, 150 DEG C, 155
DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 190 DEG C or 195 DEG C etc..
Preferably, the time of step (3) described hydro-thermal reaction be 4h-24h, for example, 5h, 6h, 7h, 8h, 9h, 10h,
12h, 13h, 15h, 18h, 20h, 22h, 23h or 24h etc..
The hydro-thermal reaction of step (3) of the present invention, using the teaching of the invention it is possible to provide high temperature and high pressure environment, it is ensured that the hydrothermal product of generation is in nanometer
Yardstick.
Preferably, methods described is additionally included in after the completion of step (3) hydro-thermal reaction, and hydrothermal product is washed, dried
The step of with sieving, the drying is preferably vacuum drying.
In the method for the present invention, the typical but non-limit of the lithium manganese phosphate presoma of the Li doping of metal ion of step (3)
Property example processed has：The lithium manganese phosphate presoma (referred to as manganese phosphate sodium lithium presoma) of Li doping of sodium ion, potassium ion Li
The lithium manganese phosphate presoma (referred to as manganese phosphate potassium lithium presoma) of doping, the lithium manganese phosphate presoma of Li doping of magnesium ion
(referred to as manganese phosphate magnesium lithium presoma), the lithium manganese phosphate presoma of Li doping of aluminium ion (is referred to as manganese phosphate aluminium lithium forerunner
Body), the lithium manganese phosphate presoma (referred to as manganese phosphate sodium-potassium-lithium presoma) of sodium ion and the common Li doping of potassium ion, sodium from
Son and the lithium manganese phosphate presoma (referred to as manganese phosphate sodium aluminium lithium presoma) of the common Li doping of aluminium ion, potassium ion, magnesium ion
With the lithium manganese phosphate presoma of aluminium ion co-doped (referred to as manganese phosphate potassium magnalium lithium presoma) etc..
As the optimal technical scheme of the method for the invention, the process of step (4) the bag carbon processing is：
The lithium manganese phosphate presoma of Li doping of metal ion is mixed to get mixed slurry, powder in a solvent with carbon source
It is broken, then dry.
Preferably, during the processing of bag carbon, the carbon source includes ascorbic acid, glucose, sucrose, citric acid, ethanol
Acid, butanedioic acid, PVA, ethylene glycol any one or at least two combination, combination typical case but non-limiting examples
Have：The combination of the combination of ascorbic acid and glucose, glucose and sucrose, the combination of sucrose, citric acid and glycolic, grape
The combination of sugar, sucrose and citric acid, butanedioic acid, PVA, the combination with ethylene glycol.But the above-mentioned carbon source enumerated is not limited to, other
Carbon source commonly used in the art can also be used for the present invention.
Preferably, bag carbon processing during, it is described metal ion Li adulterate lithium manganese phosphate presoma with it is described
The mass ratio of carbon source is 1:(0.01-0.4), for example, 1:0.05、1:0.08、1:0.10、1:0.12、1:0.15、1:0.18、1:
0.20、1:0.22、1:0.25、1:0.28、1:0.30、1:0.32、1:0.35 or 1:0.38 etc..
Preferably, during the processing of bag carbon, the solvent is absolute ethyl alcohol.
Preferably, during the processing of bag carbon, the crushing is：Ball milling, the rotating speed of the ball milling are carried out to mixed slurry
Preferably 100r/min-200r/min, for example, 100r/min, 120r/min, 140r/min, 150r/min, 160r/min,
180r/min, 190r/min or 200r/min etc., the time of the ball milling is preferably 2h-6h, for example, 2.5h, 3h, 3.5h,
4h, 4.5h, 5h or 5.5h etc..
Preferably, during the processing of bag carbon, the temperature of the drying is 50 DEG C -120 DEG C, for example, 60 DEG C, 70 DEG C, 80
DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 115 DEG C etc..
Preferably, during the processing of bag carbon, time of the drying is 5h-24h, for example, 6h, 7h, 8h, 9h, 10h,
11h, 13h, 15h, 18h, 20h or 22h etc..
Preferably, step (4) calcining is carried out in an inert atmosphere.
Preferably, the inert atmosphere is any one in nitrogen atmosphere or argon gas atmosphere.
Preferably, the temperature of step (4) described calcining be 500 DEG C -800 DEG C, for example, 520 DEG C, 530 DEG C, 540 DEG C, 550
DEG C, 580 DEG C, 600 DEG C, 630 DEG C, 650 DEG C, 680 DEG C, 700 DEG C, 730 DEG C, 750 DEG C or 780 DEG C etc..
Preferably, the time of step (4) described calcining be 2h-10h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h,
5h, 5.5h, 6h, 7h, 8h or 9h etc..
Preferably, the pattern for the composite positive pole that step (4) is obtained be near-spherical or it is spherical in any one or extremely
Few two kinds combination.
In the present invention, the pattern of composite positive pole refers to：The shape of the pattern of the primary particle of composite positive pole, i.e. crystal grain
Looks.
Preferably, the size for the composite positive pole that step (4) is obtained is in 50nm-150nm, for example, 50nm, 60nm,
65nm, 70nm, 80nm, 85nm, 90nm, 100nm, 105nm, 110nm, 120nm, 125nm, 130nm, 135nm, 145nm or
150nm etc..
In the present invention, described " size of composite positive pole refers in 50nm-150nm "：Composite positive pole is in three-dimensional side
Upward length is between 50nm-150nm.
In the present invention, the size of composite positive pole refers to：The chi of the size of the primary particle of composite positive pole, i.e. crystal grain
It is very little.
As the further preferred technical scheme of the method for the invention, it the described method comprises the following steps：
(1) by 0.5mol/L-3.0mol/L H3PO4 solution instills hydrogen-oxygen with 1mL/min-10mL/min flow rate
Change lithium and metal salt mixed solution (in the mixed solution, LiOHH2O concentration is 1.0mol/L-3.0mol/L, metal salt
Concentration be 0.1mol/L-2.0mol/L) in, obtain sediment, precipitated product washed, and be dried in vacuo, sieve, obtain white
The lithium phosphate of the Li doping of metal ion of color；
Wherein, metal salt is any one in sodium salt, sylvite, magnesium salts or aluminium salt or at least two combination；Phosphoric acid is molten
The volume ratio of liquid and lithium hydroxide and the mixed solution of metal salt is 1:2~1:5；
(2) by MnSO4·H2The lithium phosphate of Li doping of O and metal ion presses (0.5-3):1 mol ratio, is dissolved in poly- second
In the mixed solution of glycol PEG400 and water, mixed material is obtained；
Wherein, the volume ratio of polyethylene glycol PEG400 and water is (0.5-5):2；
(3) it is transferred to after mixed material is stirred vigorously in reactor, then the reactor for being contained with mixed material is put into
In homogeneous reactor, in 140 DEG C of -200 DEG C of hydro-thermal reaction 4h-24h under conditions of homogeneous reactor rotation, room temperature is cooled to,
Obtain hydro-thermal reaction product；
(4) hydro-thermal reaction product is washed, be dried in vacuo, sieving is obtained before the lithium manganese phosphate that metal ion Li adulterates
Drive body；
(5) the lithium manganese phosphate presoma of Li doping of metal ion and ascorbic acid are pressed 1:The quality of (0.01-0.4)
Than, it is sufficiently mixed in absolute ethyl alcohol, ball milling 2h-6h, 5h-24h is then dried at 50 DEG C -120 DEG C, then at 500 DEG C -800
Calcined under DEG C nitrogen atmosphere and composite positive pole is obtained after 3h-10h, natural cooling, the chemical composition of the composite positive pole
For Li1-xMxMnPO4/ C (M=Na, K, Mg, Al), x=0.001-0.4.
The third aspect, the present invention provides a kind of lithium ion battery, and the lithium ion battery includes answering described in first aspect
Close positive electrode and be used as anode active material of lithium ion battery.
Compared with the prior art, the present invention has the advantages that：
(1) present invention first prepares the lithium phosphate of Li doping of metal ion, is then added to poly- second together with manganese sulfate again
In the mixed solution of two alcohol and waters, hydro-thermal reaction is carried out, the lithium manganese phosphate presoma of Li doping of metal ion is obtained, then carried out
Bag carbon processing, calcining obtains composite positive pole Li1-xMxMnPO4/ C (any one in M=Na, K, Mg or Al or at least two
The combination planted, 0<x<1).In the composite positive pole prepared, metal ion (in Na, K, Mg or Al any one or extremely
Few two kinds of combination) doping reduce the particle size of composite positive pole, in 50nm-150nm, shortening Li+ diffusion road
Footpath, improves Li+Intercalation/deintercalation speed, improve the ionic conductivity of the metal ion mixing positive electrode, 2 layers are led
The introducing of electrical carbon layer improves associativity and electric conductivity, and composite positive pole of the invention is being highly suitable as lithium ion battery just
Pole active material, can be widely applied for field of lithium ion battery, the cycle performance and security performance of obtained lithium ion battery
Significantly improve.
(2) present invention provides new method to prepare metal ion mixing lithium manganese phosphate composite positive pole.What is provided answers
Close positive electrode Li1-xMxMnPO4/ C (in M=Na, K, Mg or Al any one or at least two combination, 0<x<1) system
Preparation Method has the advantages that technique is simple, process is easily-controllable, cost is low, yield is high, has broad application prospects.
Brief description of the drawings
Fig. 1 is Li doping LiMnPO of Na ions in embodiment 14The XRD of/C composite positive poles；
Fig. 2 is Li doping LiMnPO of Na ions in embodiment 14The SEM figures of/C composite positive poles；
Fig. 3 is Li doping LiMnPO of K ions in embodiment 24The XRD of/C composite positive poles；
Fig. 4 is Li doping LiMnPO of K ions in embodiment 24The SEM figures of/C composite positive poles；
Fig. 5 is Li doping LiMnPO of Mg ions in embodiment 34The XRD of/C composite positive poles；
Fig. 6 is Li doping LiMnPO of Mg ions in embodiment 34The SEM figures of/C composite positive poles；
Fig. 7 is Li doping LiMnPO of Al ions in embodiment 44The XRD of/C composite positive poles；
Fig. 8 is Li doping LiMnPO of Al ions in embodiment 44The SEM figures of/C composite positive poles；
Fig. 9 is Li doping LiMnPO of two metal ion species of Na, Al in embodiment 54The XRD of/C composite positive poles；
Figure 10 is Li doping LiMnPO of two metal ion species of Na, Al in embodiment 54The SEM figures of/C composite positive poles.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Battery performance test in following examples is carried out at 25 DEG C under 0.05C, and voltage tester scope is 2.5V-
4.5V, tester is Land CT2001A cell testers.
Embodiment 1
A kind of Li doping LiMnPO of Na ions4/ C composite positive poles, the composite positive pole is mixed including Na ions
Miscellaneous lithium manganese phosphate and conductive carbon layer；
Wherein, Na uniform ions are distributed in inside lithium manganese phosphate and occupy Li；With the total moles of Li ions and Na ions
Quality is 100% meter, and the molal weight percentage composition of Na ions is 10mol.%；
Described Li doping LiMnPO of Na ions4The primary particle size of/C composite positive poles is 50-100nm, pattern
For near-spherical, primary particle agglomerates into time micron ball.
Prepare：
Described Li doping LiMnPO of Na ions4The preparation method of/C composite positive poles comprises the following steps：
(1) by 0.5mol/L H3PO4The mixing that solution instills lithium hydroxide and sodium salt with 5mL/min flow rate is molten
Liquid (in the mixed solution, LiOHH2O concentration is 1.0mol/L, and the concentration of sodium salt is 0.1mol/L) in, obtain precipitation production
Thing；Precipitated product is washed, and is dried in vacuo, sieves, obtains white sodium phosphate lithium presoma powder；
(2) MnSO is taken4·H2The sodium phosphate lithium that O is synthesized with above-mentioned steps is with 1:1 mol ratio is dissolved in PEG400 and H2O's
Mixed solution (PEG400 and H2O volume ratio is 1:2) in, mixed material is obtained；
(3) after being stirred vigorously, it is transferred in reactor, the reactor for being contained with mixed material is put into homogeneous reactor
In, in after hydro-thermal reaction 6h at a temperature of the 40r/min speed of rotation, 190 DEG C, room temperature is cooled to, hydrothermal product is obtained；
(4) hydrothermal product is washed, and be dried in vacuo, sieved, obtain manganese phosphate sodium lithium presoma；
(5) by hydrothermal product manganese phosphate sodium lithium presoma and ascorbic acid with mass ratio 1:0.25 ratio is in a little anhydrous second
It is sufficiently mixed in alcohol, ball milling 2h, dries 8h at 100 DEG C, then obtains carbon after calcining 3h, natural cooling under 550 DEG C of nitrogen atmospheres
Coat manganese phosphate sodium lithium composite material, i.e., Na ions Li doping LiMnPO4/ C composite positive poles.
Test：
To obtained Li doping LiMnPO of Na ions4/ C composite positive poles carry out X-ray diffraction (XRD) test and swept
Electronic Speculum (SEM) test is retouched, test result is as depicted in figs. 1 and 2.It will be seen from figure 1 that product is the Na of pure phase olivine structural
The LiMnPO of doping4/C；Figure it is seen that the secondary micron ball that pattern is reunited for the primary particle of near-spherical.
By described Li doping LiMnPO of Na ions4/ C composite positive poles are fabricated to lithium ion cell positive and are assembled into
Battery, tests its cycle performance and capacity, and test result is that first discharge specific capacity is 147.5mAh/g under 0.05C, circulation
50 times, capability retention is 94.6%.
Embodiment 2
A kind of Li doping LiMnPO of K ions4/ C composite positive poles, the composite positive pole includes K ion dopings
Lithium manganese phosphate and conductive carbon layer；
Wherein, K uniform ions are distributed in inside lithium manganese phosphate and occupy Li；With the total moles matter of Li ions and K ions
Measure and counted for 100%, the molal weight percentage composition of K ions is 20mol.%；
Described Li doping LiMnPO of K ions4The primary particle size of/C composite positive poles is 80-150nm, and pattern is
Near-spherical, the primary particle agglomerates into time micron ball.
Prepare：
Described Li doping LiMnPO of K ions4The preparation method of/C composite positive poles comprises the following steps：
(1) by 1.5mol/L H3PO4The mixing that solution instills lithium hydroxide and sylvite with 1.5mL/L flow rate is molten
Liquid (in the mixed solution, LiOHH2O concentration is 3.0mol/L, and the concentration of sylvite is 1.0mol/L) in, obtain precipitation production
Thing；Precipitated product is washed, and is dried in vacuo, sieves, obtains white potassium phosphate powder for lithium；
(2) MnSO is taken4·H2The potassium phosphate lithium that O is synthesized with above-mentioned steps is with 3:1 mol ratio is dissolved in PEG400 and H2O's
Mixed solution (PEG400 and H2O volume ratio is 0.5:2) in, mixed material is obtained；
(3) after mixed material is stirred vigorously, it is transferred in reactor, the reactor for being contained with mixed material is put into homogeneously
In reactor, in after hydro-thermal reaction 18h at a temperature of the 60r/min speed of rotation, 145 DEG C, room temperature is cooled to, hydro-thermal production is obtained
Thing；
(4) hydrothermal product is washed, and is dried in vacuo, sieves, obtain manganese phosphate potassium lithium presoma；
(5) by hydrothermal product manganese phosphate potassium lithium presoma and ascorbic acid with mass ratio 1:0.35 ratio is in a little anhydrous second
It is sufficiently mixed in alcohol, ball milling 6h, 24h is dried at 50 DEG C, is calcined under 800 DEG C of nitrogen atmospheres and carbon bag is obtained after 5h, natural cooling
Cover manganese phosphate potassium lithium composite material, i.e., K ions Li doping LiMnPO4/ C composite positive poles.
Test：
To obtained Li doping LiMnPO of K ions4/ C composite positive poles carry out X-ray diffraction (XRD) test and swept
Electronic Speculum (SEM) test is retouched, test result is as shown in Figure 3 and Figure 4.From figure 3, it can be seen that product is the olivine structural of pure phase
K doping LiMnPO4/C；From fig. 4, it can be seen that the secondary micron ball that pattern is reunited for the primary particle of near-spherical.
By described Li doping LiMnPO of K ions4/ C composite positive poles are fabricated to lithium ion cell positive, test it and follow
Ring performance and capacity, test result are that first discharge specific capacity is 138.2mAh/g under 0.05C, are circulated 50 times, and capacity is kept
Rate is 92.8%.
Embodiment 3
A kind of Li doping LiMnPO of Mg ions4/ C composite positive poles, the composite positive pole is mixed including Mg ions
Miscellaneous lithium manganese phosphate and conductive carbon layer；
Wherein, Mg uniform ions are distributed in inside lithium manganese phosphate and occupy Li；With the total moles of Li ions and Mg ions
Quality is 100% meter, and the molal weight percentage composition of Mg ions is 5mol.%；
Described Li doping LiMnPO of Mg ions4The primary particle size of/C composite positive poles is 80-120nm, pattern
For near-spherical, the primary particle agglomerates into time micron ball.
Prepare：
Described Li doping LiMnPO of Mg ions4The preparation method of/C composite positive poles comprises the following steps：
(1) by 2.0mol/L H3PO4The mixing that solution instills lithium hydroxide and magnesium salts with 9.5mL/L flow rate is molten
Liquid (in the mixed solution, LiOHH2O concentration is 3.0mol/L, and the concentration of magnesium salts is 0.5mol/L) in, obtain precipitation production
Thing；Precipitated product is washed, and is dried in vacuo, sieves, canescence magnesium phosphate powder for lithium is obtained；
(2) MnSO is taken4·H2The magnesium phosphate lithium that O is synthesized with above-mentioned steps is with 0.5:1 mol ratio is dissolved in PEG400 and H2O
Mixed solution (PEG400 and H2O volume ratio is 5:2) in, mixed material is obtained；
(3) after mixed material is stirred vigorously, it is transferred in reactor, the reactor for being contained with mixed material is put into homogeneously
In reactor, in after hydro-thermal reaction 10h at a temperature of the 80r/min speed of rotation, 170 DEG C, room temperature is cooled to, hydro-thermal production is obtained
Thing；
(4) hydrothermal product is washed, and is dried in vacuo, sieves, obtain manganese phosphate magnesium lithium presoma；
(5) by hydrothermal product manganese phosphate magnesium lithium presoma and ascorbic acid with mass ratio 1:0.25 ratio is in a little anhydrous second
It is sufficiently mixed in alcohol, ball milling 3h, 12h is dried at 50 DEG C, is calcined under 550 DEG C of nitrogen atmospheres and carbon bag is obtained after 3h, natural cooling
Cover manganese phosphate magnesium lithium composite material, i.e., Mg ions Li doping LiMnPO4/ C composite positive poles.
Test：
To obtained Li doping LiMnPO of Mg ions4/ C composite positive poles carry out X-ray diffraction (XRD) test and swept
Electronic Speculum (SEM) test is retouched, test result is as shown in Figure 5 and Figure 6.As can be seen from Figure 5 product is pure phase olivine structural
The LiMnPO of Mg doping4/C；From fig. 6 it can be seen that the secondary micron ball that pattern is reunited for the primary particle of near-spherical.
By described Li doping LiMnPO of Mg ions4/ C composite positive poles are fabricated to lithium ion cell positive, test it
Cycle performance and capacity, test result are that first discharge specific capacity is 135.8mAh/g under 0.05C, are circulated 50 times, and capacity is protected
Holdup is 90.8%.
Embodiment 4
A kind of Li doping LiMnPO of Al ions4/ C composite positive poles, the composite positive pole is mixed including Al ions
Miscellaneous lithium manganese phosphate and conductive carbon layer；
Wherein, Al uniform ions are distributed in inside lithium manganese phosphate and occupy Li；With the total moles of Li ions and Al ions
Quality is 100% meter, and the molal weight percentage composition of Al ions is 40mol.%；
Described Li doping LiMnPO of Al ions4The primary particle size of/C composite positive poles is 50-150nm, pattern
For near-spherical, the primary particle agglomerates into time micron ball.
Prepare：
Described Li doping LiMnPO of Al ions4The preparation method of/C composite positive poles comprises the following steps：
(1) by 3mol/L H3PO4The mixing that solution instills lithium hydroxide and aluminium salt with 2.5mL/min flow rate is molten
Liquid (in the mixed solution, LiOHH2O concentration is 1.5mol/L, and the concentration of aluminium salt is 1.5mol/L) in, obtain precipitation production
Thing；Precipitated product is washed, and is dried in vacuo, sieves, white aluminum phosphate powder for lithium is obtained；
(2) MnSO is taken4·H2The aluminum phosphate lithium that O is synthesized with above-mentioned steps is with 1.0:1 mol ratio is dissolved in PEG400 and H2O
Mixed solution (PEG400 and H2O volume ratio is 4:2) in, mixed material is obtained；
(3) after mixed material is stirred vigorously, it is transferred in reactor, the reactor for being contained with mixed material is put into homogeneously
In reactor, reacted at a temperature of the 50r/min speed of rotation, 150 DEG C after 8h, be cooled to room temperature, obtain hydrothermal product；
(4) hydrothermal product is washed, and is dried in vacuo, sieves, obtain manganese phosphate aluminium lithium presoma；
(5) by hydrothermal product manganese phosphate aluminium lithium presoma and ascorbic acid with mass ratio 1:0.25 ratio is in a little anhydrous second
It is sufficiently mixed in alcohol, ball milling 4h, 12h is dried at 50 DEG C, is calcined under 500 DEG C of nitrogen atmospheres and carbon bag is obtained after 10h, natural cooling
Cover manganese phosphate aluminium lithium composite material, i.e., Al ions Li doping LiMnPO4/ C composite positive poles.
To obtained Li doping LiMnPO of Al ions4/ C composite positive poles carry out X-ray diffraction (XRD) test and swept
Electronic Speculum (SEM) test is retouched, test result is as shown in Figure 7 and Figure 8.It can be seen from figure 7 that product is pure phase olivine structural
The LiMnPO of Al doping4/C；As can be seen from Figure 8, the secondary micron ball that pattern is reunited for the primary particle of near-spherical.
By described Li doping LiMnPO of Al ions4/ C composite positive poles are fabricated to lithium ion cell positive, test it
Cycle performance and capacity, test result are that first discharge specific capacity is 142.5mAh/g under 0.05C, are circulated 50 times, and capacity is protected
Holdup is 93.8%.
Embodiment 5
A kind of Li doping LiMnPO of two metal ion species of Na, Al4/ C composite positive poles, the composite positive pole bag
Include the lithium manganese phosphate and conductive carbon layer of two kinds of ion dopings of Na, Al；
Wherein, two kinds of uniform ions of Na, Al are distributed in inside lithium manganese phosphate and occupy Li；With Li ions, Na ions and
The total moles quality of these three ions of Al ions is 100% meter, the molal weight percentage of both ions of Na ions and Al ions
Content is respectively 10mol.% and 5mol.%；
Described Li doping LiMnPO of two metal ion species of Na, Al4The primary particle size of/C composite positive poles is 30-
80nm, pattern is near-spherical, and primary particle agglomerates into time micron ball.
Prepare：
Described Li doping LiMnPO of two metal ion species of Na, Al4The preparation method of/C composite positive poles includes as follows
Step：
(1) by 1.0mol/L H3PO4Solution instills lithium hydroxide and sodium salt and aluminium salt with 7mL/min flow rate
Mixed solution (in the mixed solution, LiOHH2O concentration is 1.5mol/L, and the concentration of sodium salt and aluminium salt is respectively 1.5mol/
L and 0.75mol/L) in, obtain precipitated product；Precipitated product is washed, and is dried in vacuo, sieves, obtains white acidic sodium aluminum phosphate lithium
Presoma powder；
(2) MnSO is taken4·H2The sodium phosphate lithium that O is synthesized with above-mentioned steps is with 1:1 mol ratio is dissolved in PEG400 and H2O's
Mixed solution (PEG400 and H2O volume ratio is 1:2) in, mixed material is obtained；
(3) after being stirred vigorously, it is transferred in reactor, the reactor for being contained with mixed material is put into homogeneous reactor
In, in after hydro-thermal reaction 10h at a temperature of the 30r/min speed of rotation, 160 DEG C, room temperature is cooled to, hydrothermal product is obtained；
(4) hydrothermal product is washed, and be dried in vacuo, sieved, obtain manganese phosphate sodium aluminium lithium presoma；
(5) by hydrothermal product manganese phosphate sodium aluminium lithium presoma and ascorbic acid with mass ratio 1:0.25 ratio is a little anhydrous
It is sufficiently mixed in ethanol, ball milling 4h, dries 10h at 80 DEG C, then is obtained after calcining 5h, natural cooling under 550 DEG C of nitrogen atmospheres
Carbon coating manganese phosphate sodium aluminium lithium composite material, i.e. Li doping LiMnPO of two metal ion species of Na, Al4/C composite positive poles.
Test：
To obtained Li doping LiMnPO of two metal ion species of Na, Al4/C composite positive poles carry out X-ray diffraction
(XRD) test and ESEM (SEM) test, test result is as shown in Figure 9 and Figure 10.From fig. 9, it can be seen that product is pure phase
The LiMnPO of the metal ion species of Na, Al two doping of olivine structural4/C；From fig. 10 it can be seen that pattern is the one of near-spherical
The secondary micron ball of secondary particle aggregation.
By described Li doping LiMnPO of two metal ion species of Na, Al4/ C composite positive poles are fabricated to lithium ion battery
Positive pole is simultaneously assembled into battery, tests its cycle performance and capacity, and test result is that first discharge specific capacity is under 0.05C
143.7mAh/g, is circulated 50 times, capability retention is 92.4%.
Comparative example 1
A kind of composite positive pole and preparation method thereof, except metal ion Na dopings are lithium manganese phosphate molal weights
Outside 50mol.%, remaining is same as Example 1.
Metal ion Na doping LiMnPO4/C composite positive poles are fabricated to lithium ion cell positive, it is tested
Cycle performance and capacity, test result are that first discharge specific capacity is 98.9mAh/g under 0.05C, are circulated 50 times, and capacity is protected
Holdup is 55.7%.
Comparative example 2
A kind of composite positive pole and preparation method thereof, except metal ion K dopings are lithium manganese phosphate molal weights
Outside 50mol.%, remaining is same as Example 2.
The metal ion K doped and compounded positive electrodes are fabricated to lithium ion cell positive, test its cycle performance and
Capacity, test result is that first discharge specific capacity is 89.3mAh/g under 0.05C, is circulated 50 times, and capability retention is
61.43%.
Comparative example 3
A kind of composite positive pole and preparation method thereof, except metal ions M g dopings are lithium manganese phosphate molal weights
Outside 50mol.%, remaining is same as Example 3.
The Mg ion dopings LiMnPO4/C composite positive poles are fabricated to lithium ion cell positive, its circulation is tested
Performance and capacity, test result are that first discharge specific capacity is 91.2mAh/g under 0.05C, are circulated 50 times, capability retention
For 71.6%.
Comparative example 4
A kind of composite positive pole and preparation method thereof, except metal ion Al dopings are lithium manganese phosphate molal weights
Outside 50mol.%, remaining is same as Example 4.
The Al ion dopings LiMnPO4/C composite positive poles are fabricated to lithium ion cell positive, its circulation is tested
Performance and capacity, test result are that first discharge specific capacity is 115.7mAh/g under 0.05C, are circulated 50 times, capability retention
For 80.4%.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of composite positive pole, it is characterised in that the composite positive pole by Li doping of metal ion manganese phosphate
Lithium and be coated on it is described metal ion Li doping lithium manganese phosphate surface conductive carbon layer constitute, the metal ion be sodium
In ion, potassium ion, magnesium ion or aluminium ion any one or at least two combination.
2. composite positive pole according to claim 1, it is characterised in that the chemical composition of the composite positive pole is
Li1-xMxMnPO4/ C, wherein, in M=Na, K, Mg or Al any one or at least two combination, 0<x<1；
Preferably, the pattern of the composite positive pole be near-spherical or it is spherical in any one or at least two combination；
Preferably, the size of the composite positive pole is in 50nm-150nm；
Preferably, in the composite positive pole, the thickness of conductive carbon layer is 4nm-8nm.
3. composite positive pole according to claim 1 or 2, it is characterised in that with the Li ions and gold in composite
It is 100% meter to belong to the total moles quality of ion, and the molal weight percentage composition of the metal ion is 0.1mol.%-
40mol.%；
Preferably, counted using the gross mass of the composite as 100%, the weight/mass percentage composition of the conductive carbon layer is 1%-
40%.
4. the composite positive pole according to claim any one of 1-3, it is characterised in that the metal ion Li doping
The surface coated conductive carbon layer of lithium manganese phosphate be 2 layers of conductive carbon layer；
Preferably, being coated on two layers of conductive carbon layer on the surface of the lithium manganese phosphate of Li doping of metal ion is respectively from inside to outside
By polyethylene glycol and carbon source through calcining the conductive carbon layer being transformed；
Preferably, the carbon source is included in ascorbic acid, glucose, sucrose, citric acid, glycolic, butanedioic acid, PVA, ethylene glycol
Any one or at least two combination.
5. the preparation method of the composite positive pole as described in claim any one of 1-4, it is characterised in that methods described includes
Following steps：
(1) prepare the lithium phosphate of the doping of metal ion Li, the metal ion be sodium ion, potassium ion, magnesium ion or aluminium from
In son any one or at least two combination；
(2) lithium phosphate by the Li doping of manganese sulfate and metal ion is added in the mixed solution of polyethylene glycol and water, is obtained
Mixed material；
(3) mixed material is transferred in reactor, then the reactor for being contained with mixed material is put into homogeneous reactor, equal
Hydro-thermal reaction is carried out under conditions of the rotation of phase reaction device, the lithium manganese phosphate presoma of Li doping of metal ion is obtained；
(4) bag carbon processing is carried out to the lithium manganese phosphate presoma of Li doping of metal ion using carbon source, calcining obtains being combined just
Pole material.
6. method according to claim 5, it is characterised in that the phosphoric acid of the Li doping of metal ion described in step (1)
The pattern of lithium is any one in spherical or spherical or at least two combination；
Preferably, the size of the lithium phosphate of Li doping of the metal ion described in step (1) is in 100nm-500nm；
Preferably, the process of step (1) lithium phosphate for preparing Li doping of metal ion is：
In the mixed solution that phosphoric acid solution is added dropwise to lithium hydroxide and metal salt, sediment is obtained, this sediment is metal
The lithium phosphate of Li doping of ion；Wherein, metal salt is any one in sodium salt, sylvite, magnesium salts or aluminium salt or at least two
Combination；
Preferably, during the lithium phosphate for preparing Li doping of metal ion, the concentration of phosphoric acid solution is 0.5mol/L-
3.0mol/L；
Preferably, during the lithium phosphate for preparing Li doping of metal ion, in the mixed solution of lithium hydroxide and metal salt
Metal salt concentration be 0.1-2.0mol/L；
Preferably, during the lithium phosphate for preparing Li doping of metal ion, in the mixed solution of lithium hydroxide and metal salt
Lithium hydroxide concentration be 1.0mol/L-3.0mol/L；
Preferably, during the lithium phosphate for preparing the doping of metal ion Li, phosphoric acid solution and lithium hydroxide and metal salt
The volume ratio of mixed solution is 1:2~1:5；
Preferably, during the lithium phosphate for preparing Li doping of metal ion, the flow rate of the instillation is 1mL/min-
10mL/min；
Preferably, during the lithium phosphate for preparing Li doping of metal ion, in addition to sediment is washed, done
The step of dry and sieving, the drying is preferably vacuum drying.
7. the method according to claim 5 or 6, it is characterised in that step (2) manganese sulfate and metal ion Li are mixed
The mol ratio of miscellaneous lithium phosphate is (0.5-3):1；
Preferably, the volume ratio of step (2) polyethylene glycol and water is (0.5-5):2；
Preferably, step (2) described polyethylene glycol be PEG200, PEG400, PEG800 or PEG2000 in any one or extremely
Few two kinds combination；
Preferably, step (3) described mixed material also needs to be stirred vigorously before being transferred to reactor, described to be stirred vigorously finger
Stirring of the stir speed (S.S.) in 200r/min~400r/min；
Preferably, the rotating speed of step (3) the homogeneous reactor rotation is 40r/min-80r/min；
Preferably, the temperature of step (3) described hydro-thermal reaction is 140 DEG C -200 DEG C；
Preferably, the time of step (3) described hydro-thermal reaction is 4h-24h；
Preferably, methods described is additionally included in after the completion of step (3) hydro-thermal reaction, and hydrothermal product is washed, dried and mistake
The step of sieve, the drying is preferably vacuum drying.
8. the method according to claim any one of 5-7, it is characterised in that the process of step (4) the bag carbon processing is：
The lithium manganese phosphate presoma of Li doping of metal ion is mixed to get mixed slurry with carbon source in a solvent, crushed, so
After dry；
Preferably, during the processing of bag carbon, the carbon source includes ascorbic acid, glucose, sucrose, citric acid, glycolic, amber
In amber acid, PVA, ethylene glycol any one or at least two combination；
Preferably, bag carbon processing during, it is described metal ion Li doping lithium manganese phosphate presoma and with the carbon source
Mass ratio be 1:(0.01-0.4)；
Preferably, during the processing of bag carbon, the solvent is absolute ethyl alcohol；
Preferably, during the processing of bag carbon, the crushing is：Ball milling is carried out to mixed slurry, the rotating speed of the ball milling is preferred
For 100r/min-200r/min, the time of the ball milling is preferably 2h-6h；
Preferably, during the processing of bag carbon, the temperature of the drying is 50 DEG C -120 DEG C, and the time of the drying is preferably
5h-24h。
9. the method according to claim any one of 5-8, it is characterised in that step (4) calcining is in an inert atmosphere
Carry out；
Preferably, the inert atmosphere is any one in nitrogen atmosphere or argon gas atmosphere；
Preferably, the temperature of step (4) described calcining is 500 DEG C -800 DEG C；
Preferably, the time of step (4) described calcining is 2h-10h；
Preferably, any one during the pattern for the composite positive pole that step (4) is obtained is near-spherical or is spherical or at least two
The combination planted；
Preferably, the size for the composite positive pole that step (4) is obtained is in 50nm-150nm.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes answering described in claim any one of 1-4
Close positive electrode and be used as anode active material of lithium ion battery.
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| CN112408489A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Method for refining lithium ion battery anode material |
| CN114784283A (en) * | 2022-05-30 | 2022-07-22 | 深圳市德方纳米科技股份有限公司 | Coated positive electrode material and preparation method and application thereof |
| WO2023184496A1 (en) * | 2022-04-01 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack, and electric device |
| WO2023184493A1 (en) * | 2022-04-01 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material composition, positive electrode sheet, secondary battery, battery module, battery pack, and electrical device |
| WO2023184408A1 (en) * | 2022-03-31 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material and preparation method therefor, positive electrode plate comprising same, secondary battery and electric device |
| WO2023225796A1 (en) * | 2022-05-23 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method therefor, positive electrode sheet, secondary battery, battery module, battery pack and electric apparatus |
| WO2023245680A1 (en) * | 2022-06-24 | 2023-12-28 | 宁德时代新能源科技股份有限公司 | Positive electrode material composition and preparation method therefor, positive electrode plate comprising same, secondary battery, and electric device |
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| CN112408489A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Method for refining lithium ion battery anode material |
| CN112408489B (en) * | 2020-11-26 | 2023-01-31 | 中北大学 | Method for refining lithium ion battery anode material |
| WO2023184408A1 (en) * | 2022-03-31 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material and preparation method therefor, positive electrode plate comprising same, secondary battery and electric device |
| WO2023184496A1 (en) * | 2022-04-01 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack, and electric device |
| WO2023184493A1 (en) * | 2022-04-01 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material composition, positive electrode sheet, secondary battery, battery module, battery pack, and electrical device |
| CN116897453A (en) * | 2022-04-01 | 2023-10-17 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack, and power consumption device |
| WO2023225796A1 (en) * | 2022-05-23 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method therefor, positive electrode sheet, secondary battery, battery module, battery pack and electric apparatus |
| CN114784283A (en) * | 2022-05-30 | 2022-07-22 | 深圳市德方纳米科技股份有限公司 | Coated positive electrode material and preparation method and application thereof |
| CN114784283B (en) * | 2022-05-30 | 2024-03-29 | 深圳市德方纳米科技股份有限公司 | Coated positive electrode material and preparation method and application thereof |
| WO2023245680A1 (en) * | 2022-06-24 | 2023-12-28 | 宁德时代新能源科技股份有限公司 | Positive electrode material composition and preparation method therefor, positive electrode plate comprising same, secondary battery, and electric device |
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