CN109888208A - Anode material for lithium-ion batteries and its preparation method and application - Google Patents
Anode material for lithium-ion batteries and its preparation method and application Download PDFInfo
- Publication number
- CN109888208A CN109888208A CN201910074688.0A CN201910074688A CN109888208A CN 109888208 A CN109888208 A CN 109888208A CN 201910074688 A CN201910074688 A CN 201910074688A CN 109888208 A CN109888208 A CN 109888208A
- Authority
- CN
- China
- Prior art keywords
- lithium
- fast
- positive electrode
- preparation
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of anode material for lithium-ion batteries, including basic material and fast-ionic conductor clad, the clad is selected from lithium-titanium composite oxide, lithium zirconium mixed oxide or lithium phosphorus complex chemical compound, the basic material are selected from one of cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, LiFePO 4, nickel ion doped or lithium nickel cobalt dioxide or two or more；Raw material comprising each element in fast-ionic conductor is prepared into presoma by the present invention, surface is carried out with basic material again to merge, and solid coating film is formed through sintering, decomposition reaction of the transition elements to electrolyte is reduced while improving Ion transfer ability, and then improve the cycle life of the lithium ion battery of preparation and improve safety, it has broad application prospects.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of anode material for lithium-ion batteries and its preparation method and answers
With.
Background technique
Lithium ion conductor, as another important member in alkali-metal-ion conductor, after nineteen seventies
There is development at full speed.For late nineteen seventies to early eighties, people have found lithia and other metal oxide groups successively
At solid solution lithium ion conductivity it is very high, be expected to form a kind of new material being applied in lithium ion battery.
Lithium ion battery is widely used as due to having many advantages, such as that energy density is high, operating voltage is high, having extended cycle life
The power supply of various mobile devices, or even gradually replace other pass in the fields such as Aeronautics and Astronautics, navigation, automobile, Medical Devices
System battery.Traditional lithium ion secondary battery lithium electrolyte is dissolved with the organic of the electrolyte such as lithium hexafluoro phosphate, lithium perchlorate
Solvent has the advantages that conductivity is high, but its safety difference restricts the application space of lithium electricity, nineteen ninety Canada Moli company
As a result lithium ion battery explosion is led to, directly as electrolytic salt because lithium perchlorate thermal stability is poor using lithium perchlorate
Lithium ion battery industry is caused to enter the downhearted phase.Hereafter lithium battery industry turns to sight in the development of solid electrolyte, with
With Li3xLa2/3-xTiO3For the development of the electrolyte of representative, the room temperature developed using lithium ion conductor as diaphragm material is all solid state
Lithium battery, high security, long-life, the features such as can minimizing, attract people's attention.But since conductivity is relatively low, lithium from
Application of the sub- conductor as solid electrolyte in lithium electricity still needs to further study.
In recent years using the development of xEV new-energy automobile as the mobile power source application end of representative, to lithium ion cell high-capacity, greatly
The demand of power is increasingly urgent.To obtain higher energy density, filled often through improving positive electrode nickel content or improving battery
Electric blanking voltage is to obtain higher energy density, but high-energy density means the mistake of lithium in positive electrode in lithium ion battery
Amount is moved out；Studies have shown that lithium ion is migrated from positive electrode, transition elements price is caused to rise, transition elements is in high oxidation shape
It easily decomposes when state reaction, releases active oxygen under certain temperature；On the other hand, high oxidation state transition elements is in certain temperature
Under have a catalyticing decomposition action to the organic solvent (such as EC, DEC, PC, DMC, EMC) in electrolyte, above-mentioned factor superposition causes
The risk that lithium battery service life reduces and security performance deteriorates increases.
The main presentation for causing lithium electricity safety problem is cell heat rapid increase, occurs burning when serious or explosion phenomenon
Generation, have its source in caused by thermal runaway, i.e., battery system generate heat be greater than release heat and lead to thermal accumlation, temperature
Spend raised process rapidly.Causing the principal element of thermal runaway has: 1) internal factor, and battery positive and negative electrode material, electrolyte are stablized
Property and system adaptation are poor.Wherein it is out of control to react release heat pyrogenicity with electrolyte for cathode material structure element oxide activity height
Probability it is maximum；2) external factor, extruding, drift bolt, overheat, overcharge, the abuse conditions such as over-discharge cause electric pole short circuit and cause electrolyte
It is out of control that intensive decomposition reaction generates amount of heat pyrogenicity.
Although industry controls lithium battery work on battery manufacture by positive temperature coefficient (PTC) and other protection circuits
Battery thermal runaway phenomenon caused by temperature and current density reduce generates, but accident caused by battery itself or protective device failure
It still happens occasionally, this shows not removing a hidden danger only by increase safeguard procedures, while increasing preventive means and also improving
The use cost of lithium battery reduces the normal output of lithium battery work.
On the other hand, a major reason for causing lithium electricity service life is that the destruction of positive electrode surface texture causes；1)
Material ion itself or electron conductivity are low, and the polarization of charge and discharge process pole piece increases, so that reversible capacity declines；And electrolyte 2)
Contact the dissolution of the transition elements such as cobalt, nickel, manganese；3) structural element collapses or crystal phase changes etc., and above-mentioned positive electrode variation all may be used
Battery cycle life can be caused to decline.
Therefore lithium electricity anode is had become to improve safety, improve service life cycle by the way that the surface of positive electrode is modified
The important research field of material.
For having been commercialized the positive electrode used: cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, phosphoric acid are sub-
The modification of the types of material such as iron lithium, the lithium salts of binary acid containing manganese, common modification technology mainly has in the document reported: 1) element
Doping vario-property.Such as the methods of anion, cation or Anion-cation multiple dope, the body that can improve positive electrode is mutually conductive
Property, to avoid the structural aberration in charge/discharge cycle, inhibit transition elements disproportionated reaction and transition elements in the electrolytic solution
Dissolution.As Chinese patent CN200610031706.X discloses the lithium battery anode material of secondary deposition method preparation doping multiple element
The method of material, carries out Al, Mg, Ti in positive electrode, at least two species complexities and cladding in Cr element, then post-treated to obtain
Obtain doping vario-property positive electrode.Chinese patent CN200910020749.1 discloses a kind of manganese layer position niobium of lithium ion secondary battery
Doping type lithium manganate positive electrode and preparation method thereof carries out manganic niobium doping, preparation two using the solid phase method for being easy to industrialization
Secondary lithium ion battery lithium manganate material.2) compound coating modification.Predominantly Al, Ti, Mg, Zr, Zn, Ag, rare earth, transition member
Packet of the compounds such as oxide, hydroxide, phosphate, silicate, the fluoride of the elements such as element in positive electrode powder surface
It covers.Main purpose reduces corrosion of the electrolyte to positive electrode surface.As Chinese patent CN201410209996.7 discloses one
Kind of mixing anode material of lithium battery and preparation method thereof, cobalt oxide, ternary precursor and lithium salts hybrid reaction are formed, obtain by
The microstructure of cobalt acid lithium particles coat nickle cobalt lithium manganate particle.3) polycrystallization is modified.By by the material of different crystal phase structures
It is mixed by mechanical, chemistry or thermodynamic condition, changes the charging and discharging curve and platform of battery, reduce transition elements oxidation
Activity reduces the generation of transition elements disproportionated reaction.As Chinese patent ZL 200910110132.9 discloses polycrystal Co-Ni-Mn three
First positive electrode and preparation method thereof, it is compound to be that the material that will have complete crystal phase structure carries out under thermal condition, completes
The polycrystallization of integral material.Chinese patent ZL20091018197.7 discloses high-manganese polycrystalline cathode material and preparation method thereof,
It is modified that polycrystallization is carried out by the LiMn2O4 to spinel structure.
Summary of the invention
Technical problem solved by the present invention is existing anode material for lithium ion battery is in use process although by not
The security performance and chemical property of the lithium ion battery of preparation are improved with the improvement of approach, but because the structure of bulk material lacks
It falls into, can not prevent and improve the security performance and chemical property of lithium ion from basic reason, therefore urgently develop one kind
The improved method of new simple possible.
In order to solve the above technical problems, the present invention is based on the ionic conductance performances of ion conductor on existing positive electrode surface
Upper formation solid-state conductive film improves positive electrode interface while reducing electrolyte and high oxidation state positive electrode surface contacts
Ionic conductivity improves battery, improves safety.The chemical property for not influencing ontology positive electrode simultaneously, with
Prior art is different.
Positive electrode of the present invention consists of two parts: basic material and interface fusion solid film composition, basic material are
Know positive pole material of lithium cobalt acid, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, LiFePO 4, nickel ion doped or the nickel of commercialization
Cobalt acid lithium, interface fusion solid membrane material composition are Li and Ti, La, Zr, Sr, Y, Co, Mn one of which or two or more elements
The oxide or phosphate of composition.
Positive electrode of the present invention consists of two parts: basic material and interface fusion solid film composition, basic material are
Know positive pole material of lithium cobalt acid, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, LiFePO 4, nickel ion doped or the nickel of commercialization
Cobalt acid lithium, interface fusion solid membrane material composition are Li and Ti, La, Zr, Al, Sr, Y, Co, Mn one of which or two or more members
The oxide or phosphate of element composition generate fast-ionic conductor product including but not limited to LiMTiO4、LiMZrO4、LiMTiPO4、
LiMZrPO4Equal lithium-containing compounds, wherein M is Ti, La, Zr, Sr, Al, Y, Co, Mn one of or two or more, and structure is shown
Meaning is as shown in Figure 1.Fusion solid film, that is, fast-ionic conductor the clad.
Compared with prior art, the main distinction is it is not to carry out element doping or single to positive electrode prepared by the present invention
Oxide surface cladding, but the element that can be made into fast-ionic conductor is prepared into presoma, and just by the presoma and basis
Pole material carries out surface fusion, and forms solid coating film through sintering, and transition member is reduced while improving Ion transfer ability
Decomposition reaction of the element to electrolyte, and then improve the cycle life of the lithium ion battery of preparation and improve safety.
Specifically, in view of the deficiencies of the prior art, the present invention provides the following technical scheme that
A kind of anode material for lithium-ion batteries, which is characterized in that described including basic material and fast-ionic conductor clad
Clad is selected from following any:
(1) lithium-titanium composite oxide, chemical formula are (Li2O)x-(MαO2)y-(TiO3)z, M element be selected from cobalt, zirconium, lanthanum, aluminium,
The one or more of strontium, manganese or yttrium,
(2) lithium zirconium mixed oxide, chemical formula are (Li2O)x-(MαO2)y-(ZrO3)z, M element be selected from cobalt, titanium, lanthanum, aluminium,
The one or more of strontium, manganese or yttrium,
(3) lithium phosphorus complex chemical compound, chemical formula are (Li2O)x-(MαO2)y-(PO4)z, M element be selected from cobalt, zirconium, titanium, lanthanum,
The one or more of aluminium, strontium, manganese or yttrium, and M includes at least the one or two of titanium or zirconium；
Wherein, 0.1≤x≤1.5,0.3≤α≤2.5,0 < y≤2.0,0.1≤z≤4；
The basic material is selected from cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, LiFePO 4, nickel mangaic acid
One of lithium or lithium nickel cobalt dioxide are two or more.
Preferably, in above-mentioned positive electrode, 0.1≤(2x+ α y)/z≤5.0.
Preferably, in above-mentioned positive electrode, 0.1≤x≤1.0.
Preferably, in above-mentioned positive electrode, 1.0≤α≤2.0.
Preferably, in above-mentioned positive electrode, 0 y≤1.5 <.
Preferably, in above-mentioned positive electrode, 0.5≤z≤2.0.
Preferably, in above-mentioned positive electrode, 1.0≤z≤2.0.
Preferably, in above-mentioned positive electrode, M element is preferably zirconium, cobalt, aluminium, the one or more of lanthanum, manganese or yttrium.
Preferably, in above-mentioned positive electrode, when clad is lithium-titanium composite oxide, M is selected from lanthanum, aluminium, manganese or yttrium
The one or more of one or more, preferably aluminium, strontium, lanthanum.
Preferably, in above-mentioned positive electrode, when clad is lithium zirconium mixed oxide, M is selected from cobalt, aluminium, strontium or manganese
The one or two of one or more, preferably cobalt or strontium.
Preferably, in above-mentioned positive electrode, when clad is lithium phosphorus complex chemical compound, M is selected from one kind of titanium, cobalt or lanthanum
Or it is two or more, and include at least titanium.
Preferably, in above-mentioned positive electrode, the mass ratio of the basic material and fast-ionic conductor clad is (60-
95): (5-40), it is preferred that the mass ratio of the basic material and fast-ionic conductor clad is (75-95): (5-25).
Preferably, in above-mentioned positive electrode, the mass ratio of the basic material and fast-ionic conductor clad is (80-
95): (5-20).
Preferably, in above-mentioned positive electrode, the median (D of the positive electrodev50):2-25μm。
The present invention also provides the preparation methods of above-mentioned anode material for lithium-ion batteries, which is characterized in that includes the following steps:
(1) raw material comprising fast-ionic conductor clad each element and polyketone resinoid are subjected to mixed dissolution, after dry
Obtain fast-ionic conductor precursor compound.
(2) composite drying: being configured to colloidal sol for deionized water and thickener, is uniformly mixed after fast-ionic conductor is added,
Then basic material is added, obtains mixture after dry；
(3) it is sintered: mixture obtained by step (2) being sintered at 650-1000 DEG C, obtains the positive electrode.
Preferably, in step (1), after mixed dissolution further include: the process for adding lithium salts, the elemental lithium added with fastly from
The molar ratio of elemental lithium is (0.1-1.5): 1, preferably (0.1-1): 1 in sub- conductor clad.
Preferably, in above-mentioned preparation method, the raw material total amount and polyketone comprising fast-ionic conductor clad each element
The mass ratio of resinoid is (1-15): 1.
Preferably, in above-mentioned preparation method, in step (2), the mass ratio of the deionized water and thickener is 100:
(0.2-4.0), preferably 100:(0.5-1.5).
Preferably, in above-mentioned preparation method, in step (2), the mass ratio of the deionized water and fast-ionic conductor is
100:(5-100), preferably 100:(10-55).
Preferably, in above-mentioned preparation method, the thickener is selected from sodium carboxymethylcellulose (CMC), hydroxyethyl cellulose
(HEC), the one or more of hydroxypropyl cellulose or polyvinyl alcohol (PVA).
Preferably, in above-mentioned preparation method, the raw material comprising fast-ionic conductor clad each element is selected from the oxygen of each element
Compound, hydroxide, carbonate, sulfate, nitrate, acetate or phosphatic one or more.
Preferably, in above-mentioned preparation method, the raw material comprising elemental lithium is selected from monohydrate lithium hydroxide, lithium chloride, vinegar
The one or more of sour lithium or lithium sulfate, preferably monohydrate lithium hydroxide.
Preferably, in above-mentioned preparation method, the raw material comprising titanium elements is selected from nano-titanium dioxide, lithium titanate, phosphorus
The one or more of sour titanium, Titanium pyrophosphate, butyl titanate, titanium colloidal sol or nano-metatitanic acid, preferably nanometer titanium dioxide
Titanium.
Preferably, in above-mentioned preparation method, the raw material comprising zr element is selected from nanometer zirconium hydroxide, nano oxidized
The one or more of zirconium, basic zirconium phosphate, zirconium nitrate, zirconium-n-propylate or zirconium colloidal sol, preferably nanometer zirconium hydroxide.
Preferably, in above-mentioned preparation method, the raw material comprising lanthanum element is selected from nano lanthanum oxide, lanthanum orthophosphate or nanometer
The one or more of lanthanum hydroxide, preferably Nano-lanthanum hydroxide or lanthanum orthophosphate.
Preferably, in above-mentioned preparation method, the polyketone resinoid can be dissolved in water but also be dissolved in organic solvent, preferably
Polyvinylpyrrolidone.
Preferably, in above-mentioned preparation method, the temperature of drying process described in step (1) is 80-150 DEG C, time 1-
10h。
Preferably, in above-mentioned preparation method, drying process temperature described in step (2) is 105-180 DEG C, time 1-
10h。
Preferably, in above-mentioned preparation method, calcining time is 3-10h in step (3).
Preferably, in above-mentioned preparation method, the sintering process needs to be passed through oxygen rich gas, and the volume content of oxygen is
45-99.9%, the flow of oxygen rich gas are 5-500Nm3/h。
Preferably, in above-mentioned preparation method, the median of the fast-ionic conductor is (Dv50): 5-500nm.The base
Median (the D of plinth materialv50):2-25μm。
The present invention also provides a kind of anode material for lithium-ion batteries, are prepared by the above method.
The present invention also provides a kind of lithium ion batteries, including above-mentioned positive electrode.
The present invention also provides above-mentioned positive electrode or above-mentioned lithium ion battery lithium electric energy source domain application.
The invention has the advantages that the present invention is based on the ionic conductance performances of ion conductor on existing positive electrode surface shape
At solid-state conductive film, while reducing electrolyte and high oxidation state positive electrode surface contacts, improve positive electrode interface ion
Conductivity improves battery, improves safety.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of positive electrode of the present invention.
Fig. 2-a, Fig. 2-b, Fig. 2-c and Fig. 2-d are respectively the scanning of comparative example 1, comparative example 2, embodiment 1 and embodiment 2
The amplification factor of electron microscope, Fig. 2-a and Fig. 2-c are 3000 times, and the amplification factor of Fig. 2-b and Fig. 2-d are 5000 times.
Fig. 3 is the electrochemistry of embodiment lithium battery 1, embodiment lithium battery 4, comparative example lithium battery 1 and comparative example lithium battery 3
Impedance spectra.
Fig. 4-a and Fig. 4-b is respectively embodiment lithium battery 1 and 1 sting voltage of comparative example lithium battery and temperature rise change curve.
Specific embodiment
Uneven in view of lithium diffusion in current anode material for lithium-ion batteries, the lithium content that dissociates is high, leads to cathode material structure
Stability is poor, the lithium ion battery gas production of preparation big the problems such as limiting its application field, and the present invention, which provides, a kind of prepares lithium
The method of ion positive electrode, by preparing fast-ionic conductor predecessor and adding polymer and be mixed together again with bulk material
Afterwards, through drying, it is sintered the lithium ion battery material of in-situ preparation fast-ionic conductor cladding, is conducive to the object for promoting positive electrode
Reason and chemical property, expand the application field of the positive electrode.Technique preparation is simple, can be combined together doping process
Preparation uniformity is good, and crystal structure is complete, and dissociate the low material of lithium content, is conducive to the business application for expanding lithium ion battery.
In a kind of preferred embodiment, the present invention, which provides, a kind of prepares the uniform cladded type lithium ion anode of fast-ionic conductor
The method of material, by mixing fast-ionic conductor with bulk material finished product either semi-finished product again after mixing in dispensing stage
It closes, drying, sintering, crushing obtains fast-ionic conductor clad anode material finished product.
Wherein, above-mentioned fast-ionic conductor presoma refers to that the raw material for producing fast-ionic conductor after sintering uniformly mixes
Object, it is poly- in presoma and a small amount of bonding agent of bulk material compound tense addition to form tentatively firm forerunner's qualification coating needs
Vinylpyrrolidone.
Preferably, above-mentioned polyvinylpyrrolidone bonding agent, the raw material total amount comprising fast-ionic conductor clad each element
Mass ratio with polyketone resinoid is (1-15): 1.
The present invention relates to field of lithium ion battery, and in particular to through lithium fast-ionic conductor handle positive electrode and its answer
With, and in particular to technology is inorganic non-metallic material sintering synthesis.Lithium ion conductor and positive electrode are subjected to interface fusion, reached
To raising lithium electricity cycle life and improve safety purpose.
The fast-ionic conductor is lithium-titanium composite oxide (Li2O)x-(MαO2)y-(TiO3)z, lithium zirconium mixed oxide
(Li2O)x-(MαO2)y-(TiO3)zOr lithium phosphorus complex chemical compound (Li2O)x-(MαO2)y-(PO4)z, lithium-titanium composite oxide
(Li2O)x-(MαO2)y-(TiO3)z, lithium zirconium mixed oxide (Li2O)x-(MαO2)y-(TiO3)zWith spinel-type solid knot
Structure has three-dimensional ion channel.Lithium phosphorus complex chemical compound (Li2O)x-(MαO2)y-(PO4)zIt is same to have with olivine structure
There is three-dimensional ion channel structure, be fast ion conducting material, there is preferable ion ducting capacity.Positive electrode is cobalt acid
Lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, LiFePO 4, nickel ion doped or lithium nickel cobalt dioxide etc..Lithium will first be generated
The material of ion conductor is uniformly mixed, then is mixed with basic material and obtained through sintering/pulverization process.The preparation method economy can
Row, applicability is extensive, and effect is obvious, with good application prospect.
In another preferred embodiment, the present invention provides a kind of preparation side of lithium ion conductor positive electrode for battery material
Method, which is characterized in that prepare, mixed with positive bulk material and positive electrode lithium ion including nano-lithium ion conductor precursor body
The processes such as conductor crystal boundary sintering fusion.Preparation method is as follows.
1) by presoma lithium salts, fast-ionic conductor raw material, aqueous polyketone resin carries out mixed dissolution, then mixes through high speed dispersion
Slurry is prepared into after conjunction.A small amount of lithium salts is added into slurry or do not added to reselection, by slurry in 80-150 DEG C of dry 1-
10h dehydration, keeps water content in 5-20%, obtains fast-ionic conductor presoma object.
2) composite drying.By deionized water: CMC=100:(0.2-4) weight ratio prepare colloidal sol, before having prepared
It drives body to be added after mixing evenly, commercialization positive electrode is then added, 30- is dispersed using kneader either helical-ribbon type batch mixer
60min then takes out in 105-180 DEG C of dry 1-10h.
3) it is sintered.The material of above-mentioned drying is fitted into and is put into program in high-temperature sintering apparatus in ceramic alms bowl and is warming up to 650-
1000 DEG C of processing 3-10h take out ball mill grinding and obtain contrivance lithium fast-ionic conductor positive electrode for battery material.
Preferably, in above-mentioned steps (1), the molar ratio of the elemental lithium and elemental lithium in fast-ionic conductor clad added is
(0.1-1.5): 1, preferably (0.1-1): 1.
Preferably, in above-mentioned preparation method, the presoma is to produce lithium-titanium composite oxide (Li2O)x-(MαO2)y-
(TiO3)z, lithium zirconium mixed oxide (Li2O)x-(MαO2)y-(ZrO3)zEither lithium phosphorus complex chemical compound (Li2O)x-(MαO2)y-
(PO4)z, it is also possible to the colloid of above-mentioned composition；Wherein x=0.1-1.5,0 < y≤2.0, z=0.1-4, M is zirconium (Zr), lanthanum
(La), the above element of at least one of aluminium (Al), strontium (Sr), yttrium (Y), cobalt (Co) or manganese (Mn).The preferred zirconium of M element (Zr), lanthanum
(La), one or more of yttrium (Y) element.
Preferably, in above-mentioned preparation method, the lithium salts is that soluble lithium salt includes monohydrate lithium hydroxide, lithium chloride, vinegar
It is more than at least one of preferred lithium hydroxide of sour lithium, lithium sulfate.
Preferably, in above-mentioned preparation method, the titanium salt be nano-titanium dioxide, titanium colloidal sol, nano-metatitanic acid etc. extremely
Few one kind, preferably nano-titanium dioxide, zirconates are nanometer zirconium hydroxide, nano zircite, basic zirconium phosphate, zirconium colloidal sol, preferably nanometer
Zirconium hydroxide, lanthanum salt are as follows: nano lanthanum oxide, lanthanum orthophosphate, Nano-lanthanum hydroxide, excellent nanometer select lanthana, lanthanum orthophosphate.
Preferably, in above-mentioned preparation method, in the presoma dispersing aid be aqueous polyketone resinoid, solvent be go from
Sub- water, the polyketone resinoid are that can be dissolved in water but also be dissolved in the organic matter of organic solvent, such as polyvinylpyrrolidone
(PVP)。
Preferably, in above-mentioned preparation method, the dry equipment used of the slurry is that jacket type pinches full machine, rotary kiln, drum
Wind baking oven etc., heat medium are conduction oil, vapor etc., and drying temperature is 80-150 DEG C/1-10h.
Preferably, it in above-mentioned preparation method, needs that a small amount of bonding agent carboxylic is added in forerunner's qualification and ontology compound tense, such as
Sodium carboxymethylcellulose pyce (CMC), additive amount is in deionized water: CMC=100:(0.2-4) ratio prepare colloidal sol after add.
Preferably, in above-mentioned preparation method, presoma and ontology positive electrode are using kneader either helical-ribbon type mixing
Machine dispersion, jitter time 30-60min are prepared into the slurry of certain fluidity either quasi- mobility, then by slurry through 120-
180 DEG C/1-10h is dried for standby.
Preferably, in above-mentioned preparation method, the sintering fruit process needs to be passed through oxygen-enriched atmosphere, and the volume content of oxygen is
45-99.9%.The flow of oxygen is 5-500Nm3/h。
Preferably, in above-mentioned preparation method, the bulk material is cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, mangaic acid
One of lithium, LiFePO 4, nickel ion doped or lithium nickel cobalt dioxide or more than one.
Preferably, in above-mentioned preparation method, the mass ratio of the bulk material and presoma fast ion conducting material is
(60-95): (5-40).
Preferably, in above-mentioned preparation method, the partial size of the fast-ionic conductor is (Dv50): 5-500nm.The ontology material
Partial size (the D of materialv50):2-25μm。
Preferably, in above-mentioned preparation method, high-temperature sintering apparatus is ventilation Muffle furnace, roller kilns, pushed bat kiln etc..
The present invention also provides a kind of lithium ion conductor positive electrode for battery materials, which is characterized in that by above-mentioned preparation method system
It is standby to obtain.
The present invention also provides a kind of lithium ion batteries, which is characterized in that includes above-mentioned lithium ion conductor positive electrode for battery material
Material.
The present invention also provides above-mentioned lithium ion conductor positive electrode for battery materials or above-mentioned lithium ion battery to lead in lithium electric energy
The application in domain.
Anode material for lithium-ion batteries of the present invention and its preparation method are further illustrated below by specific embodiment.
In the following embodiments, the information of each reagent used and instrument is as follows:
Agents useful for same information in 1 embodiment of the present invention of table
Device therefor information in 2 embodiment of the present invention of table
Embodiment 1
It weighs 23.3kg monohydrate lithium hydroxide to be added in 500L coulter type mixer, opens stirring and the poly- second of 100kg is added
Alkene pyrrolidone and 40kg deionized water add 91.6kg titanium dioxide and 105.85kg lanthanum hydroxide after stirring sufficiently,
It will be then transferred in pallet to be put into baking oven after material stirring 50min and be toasted 2 hours in 105 DEG C, keep material moisture content content about
5% obtains in fluffy fast-ionic conductor solid material 1.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg sodium carboxymethylcellulose, then plus
10kg solid material 1 is added after entering 100kg lithium cobaltate cathode material stirring 20min, after mixing 30min, slurry is poured into
It is put into pallet in drying box and dries to obtain solid block material in 120 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 45%, gas input 400m3/ h), 650 DEG C of processing material 10h are warming up to, material is after cooling through cyclone vortex powder
Broken machine is crushed, and humidity≤2% of surrounding air is controlled when crushing, and is sieved to obtain the fast ion of object lithium of the present invention through 300 mesh
Conductor positive electrode for battery material.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 15 μm, specific surface area is
0.8m2/g。
With ICP to the results are shown in Table 3 after the quantitative elementary analysis of positive electrode, the structural formula of material is prepared through accounting
Are as follows: LiCoO2·0.035Li0.5La0.5TiO3, lithium-titanium composite oxide structural formula is (Li2O)0.25-(La2O3)0.25-TiO3。
Positive electrode element characterization result described in 3 embodiment 1 of table
| Element | Li | Co | Al | Ca | Mg | La |
| Mass ratio | 7.25 | 60.55 | 0.0198 | 0.002 | 0.0024 | 2.2217 |
| Atomic weight | 6.94 | 58.93 | 26.98 | 40 | 24 | 138.91 |
| Molal quantity | 1.04 | 1.03 | 0.0007 | 0.00005 | 0.0001 | 0.016 |
| Element | P | S | Ti | Y | Zn | Zr |
| Mass ratio | 0.0047 | 0.0547 | 1.398 | 0.021 | 0 | 0.0023 |
| Atomic weight | 30.97 | 32 | 40 | 88.91 | 65.41 | 91.22 |
| Molal quantity | 0.00015 | 0.00171 | 0.035 | 0.0002 | 0 | 0.00003 |
Embodiment 2
42.6kg lithium carbonate is weighed to be added in 500L kneader, open stirring be added 30kg polyvinylpyrrolidone and
40kg deionized water adds 34.29kg metatitanic acid and 52.61kg lithium titanate (Li after stirring sufficiently4Ti5O12), and
17.94kg aluminium hydroxide.It will be then transferred in pallet and be put into baking oven in 150 DEG C of baking 1.5h after material stirring 50min, kept
Material moisture content content about 20% obtains blocks of solid material 2.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg sodium carboxymethylcellulose, then plus
20kg solid material 2 is added after entering 100kg manganate cathode material for lithium stirring 20min, after mixing 30min, slurry is poured into
It is put into pallet in drying box and dries to obtain solid block material in 150 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 45%, gas input 200m3/ h), 860 DEG C of processing material 10h are warming up to, material is after cooling through ceramic ball mill
It crushes, controls humidity≤2% of surrounding air when crushing, and be sieved to obtain object fast ion conductor battery of the present invention through 300 mesh and use
Positive electrode.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 9.3 μm, specific surface area is
1.4m2/g.With ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows: LiMn2O4·
0.188Li1.25Al0.25TiO3, lithium-titanium composite oxide structural formula is (Li2O)0.625-(Al2O3)0.125-TiO3。
Embodiment 3
It weighs 33.61kg monohydrate lithium hydroxide to be added in 500L fusion machine, opens stirring and 60kg polyvinyl pyrrole is added
Alkanone and 40kg deionized water add 90.61kg Titanium pyrophosphate TiP after stirring sufficiently2O7.It will turn again after material stirring 50min
It moves on in pallet and is put into baking oven in 105 DEG C of baking 1.5h, material moisture content content about 10% is kept to obtain blocks of solid material 3.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg sodium carboxymethylcellulose, then plus
Enter 100kg nickel-cobalt lithium manganate cathode material (LiNi0.5Co0.2Mn0.3O2) stirring 20min after add 28kg solid material 3, mix
After closing 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 70%, gas input 400m3/ h), 850 DEG C of processing material 12h are warming up to, material is after cooling through cyclone vortex powder
Broken machine is crushed, and controls humidity≤2% of surrounding air when crushing, and is sieved to obtain the fast ion of object of the present invention through 300 mesh and be led
Body positive electrode for battery material.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 10.3 μm, specific surface area is
0.6m2/ g, with ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows:
LiNi0.5Co0.2Mn0.3O2·0.06Li2Ti(PO4)2, lithium composite phosphorus oxide structural formula is (Li2O)-(TiO2)-(PO4)2。
Embodiment 4
36.29kg lithium acetate is weighed to be added in 500L kneader, open stirring be added 50kg polyvinylpyrrolidone and
40kg deionized water adds tri- water manganese sulfate of 43.1kg metatitanic acid and 29.46kg after stirring sufficiently.By material stirring
It is then transferred in pallet and is put into baking oven in 120 DEG C of baking 1.0h after 50min, material moisture content content about 15% is kept to obtain bulk
Solid material 4.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg sodium carboxymethylcellulose, then plus
Enter 100kg nickel cobalt lithium aluminate cathode material (LiNi0.8Co0.15Al0.05O2) stirring 20min after add 25kg solid material 4, mix
After closing 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 95%, gas input 300m3/ h), 830 DEG C of processing material 8h are warming up to, material is after cooling through cyclone vortex powder
Broken machine is crushed, and controls humidity≤2% of surrounding air when crushing, and is sieved to obtain the fast ion of object of the present invention through 300 mesh and be led
Body positive electrode for battery material.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 7.3 μm, specific surface area is
1.4m2/g.With ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows:
LiNi0.8Co0.15Al0.05O2·0.08Li1.25Mn0.25TiO3Lithium-titanium composite oxide structural formula is (Li2O)0.625-
(Mn2O3)0.125-(TiO3)。
Embodiment 5
21.83kg lithium carbonate is weighed to be added in 500L kneader, open stirring be added 70kg polyvinylpyrrolidone and
40kg deionized water adds five water zirconium nitrate of 69.0kg cobalt carbonate and 196.6kg after stirring sufficiently.By material stirring
It is then transferred in pallet and is put into baking oven in 120 DEG C of baking 1.5h after 50min, material moisture content content about 20% is kept to obtain bulk
Solid material 5.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg sodium carboxymethylcellulose, then plus
25kg solid material 5 is added after entering 100kg lithium iron phosphate cathode material stirring 20min, after mixing 30min, slurry is fallen
Enter to be put into pallet in drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through appropriate air (300Nm3/
H), 730 DEG C of processing material 8h are warming up to, material is crushed through ceramic ball mill after cooling, and control surrounding air is wet when crushing
Degree≤2%, and be sieved to obtain object fast ion conductor battery positive electrode of the present invention through 300 mesh.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 2.3 μm, specific surface area is
5.2m2/g.With ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows: LiFePO4·
0.064LiCoZrO4, lithium zirconium mixed oxide structural formula is (Li2O)0.5-(Co2O3)0.5-(ZrO3)。
Embodiment 6
It weighs 2.52kg monohydrate lithium hydroxide to be added in 500L coulter type mixer, opens stirring and the poly- second of 100kg is added
Alkene pyrrolidone and 40kg deionized water add tetra- water acetic acid yttrium of 38.52kg and 340.4kg metatitanic acid four after stirring sufficiently
Butyl ester (20% content) will be then transferred in pallet to be put into baking oven after material stirring 50min and toast 2 hours in 105 DEG C, keeps
Material moisture content content about 5% is obtained in fluffy fast-ionic conductor solid material 6.
130kg deionized water is added in kneader, after adding the dissolution completely of 1.0kg sodium carboxymethylcellulose, then plus
Enter 100kg nickel lithium manganate cathode material (LiNi0.5Mn1.5O2) stirring 20min after add 13.9kg solid material 6, mix
After 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 120 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 45%, gas input 400Nm3/ h), 860 DEG C of processing material 7h are warming up to, material is after cooling through cyclone vortex powder
Broken machine is crushed, and is sieved to obtain object lithium fast-ionic conductor positive electrode for battery material of the present invention through 300 mesh.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 6.0 μm, specific surface area is
1.4m2/g。
With ICP to the results are shown in Table 3 after the quantitative elementary analysis of positive electrode, the structural formula of material is prepared through accounting
Are as follows: LiNi0.5Mn1.5O2·0.02Li0.3Y0.57TiO3, lithium-titanium composite oxide structural formula is (Li2O)0.15-(Y2O3)0.26-
TiO3。
Embodiment 7
It weighs 4.71kg lithium carbonate to be added in 500L coulter type mixer, opens stirring and 100kg polyvinyl pyrrole is added
Alkanone and 40kg deionized water add 53.24kg strontium carbonate and 47.94kg titanium dioxide after stirring sufficiently, material are stirred
It mixes to be then transferred in pallet after 50min to be put into baking oven and be toasted 2 hours in 105 DEG C, keep the material moisture content content about 5% to be in
Fluffy fast-ionic conductor solid material 7.
90kg deionized water is added in kneader, after adding the dissolution completely of 1.3kg sodium carboxymethylcellulose, adds
100kg lithium nickel cobalt dioxide positive electrode (LiNi0.5Co1.5O2) 13.2kg solid material 7 is added after stirring 20min, mix 30min
Afterwards, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 120 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 45%, gas input 400m3/ h), 1000 DEG C of processing material 6h are warming up to, material is after cooling through cyclone vortex powder
Broken machine is crushed, and is sieved to obtain object lithium fast-ionic conductor positive electrode for battery material of the present invention through 300 mesh.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 16 μm, specific surface area is
0.4m2/g。
With ICP to the results are shown in Table 3 after the quantitative elementary analysis of positive electrode, the structural formula of material is prepared through accounting
Are as follows: LiNi0.5Co1.5O2·0.06Li0.21Sr0.6TiO3, lithium-titanium composite oxide structural formula is (Li2O)0.1-(Sr2O3)0.3-
TiO3。
Embodiment 8
It weighs 50.031kg monohydrate lithium hydroxide to be added in 500L fusion machine, opens stirring and 60kg polyvinyl pyrrole is added
Alkanone and 40kg deionized water add 58.8kg titanium dioxide and 140.5kg lanthanum orthophosphate after stirring sufficiently.Material is stirred
It mixes to be then transferred in pallet after 50min and be put into baking oven in 105 DEG C of baking 1.5h, material moisture content content about 10% is kept to obtain block
Shape solid material 8.
100kg deionized water is added in kneader, after adding the dissolution completely of 1.1kg carboxyethyl cellulose, adds
100kg nickel-cobalt lithium manganate cathode material (LiNi0.6Co0.2Mn0.2O2) stirring 20min after add 32kg solid material 8, mix
After 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 70%, gas input 400Nm3/ h), 690 DEG C of processing material 12h are warming up to, material is after cooling through cyclone vortex
Pulverizer is crushed, and is sieved to obtain object fast ion conductor battery positive electrode of the present invention through 300 mesh.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 9.7 μm, specific surface area is
0.9m2/ g, with ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows:
LiNi0.6Co0.2Mn0.6O2·0.06Li2LaTi(PO4)3, lithium composite phosphorus oxide structural formula is (Li2O)-(TiO2)-
(La2O3)0.5-(PO4)3。
Embodiment 9
44.41kg lithium carbonate is weighed to be added in 500L fusion machine, open stirring be added 60kg polyvinylpyrrolidone and
40kg deionized water adds 55.9kg hydroxide cobalt and 219.88kg titanium phosphate after stirring sufficiently.By material stirring
It is then transferred in pallet and is put into baking oven in 105 DEG C of baking 1.5h after 50min, material moisture content content about 10% is kept to obtain bulk
Solid material 9.
140kg deionized water is added in kneader, after adding the dissolution completely of 0.7kg sodium carboxymethylcellulose, then plus
Enter 100kg nickel-cobalt lithium manganate cathode material (LiNi0.7Co0.15Mn0.15O2) stirring 20min after add 19.2kg solid material 9,
After mixing 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through oxygen-enriched air (oxygen content body
Product is than being 70%, gas input 400Nm3/ h), 850 DEG C of processing material 12h are warming up to, material is after cooling through cyclone vortex
Pulverizer is crushed, and humidity≤2% of surrounding air is controlled when crushing, and is sieved to obtain the fast ion of object of the present invention through 300 mesh
Conductor positive electrode for battery material.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 3.2 μm, specific surface area is
0.7m2/ g, with ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows:
LiNi0.7Co0.15Mn0.15O2·0.06LiCo0.5Ti(PO4)3, lithium composite phosphorus oxide structural formula is (Li2O)0.5-
(Co2O3)0.25-(TiO2)-(PO4)3。
Embodiment 10
It weighs 20.95kg monohydrate lithium hydroxide to be added in 500L kneader, opens stirring and 70kg polyvinyl pyrrole is added
Alkanone and 40kg deionized water add 25.59kg aluminum oxide and 163.88kg zirconium-n-propylate after stirring sufficiently.It will
It is then transferred in pallet and is put into baking oven in 120 DEG C of baking 1.5h after material stirring 50min, keep material moisture content content about 20%
Obtain blocks of solid material 10.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg carboxy-propyl cellulose, adds
100kg nickel-cobalt lithium manganate cathode material (LiNi0.8Co0.1Mn0.1O2) stirring 20min after add 29.1kg solid material 10, mix
After closing 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through appropriate air (oxygen content body
Product is than being 80%, gas input 300Nm3/ h), 650 DEG C of processing material 8h are warming up to, material is after cooling through ceramic ball mill
It crushes, controls humidity≤2% of surrounding air when crushing, and be sieved to obtain object fast ion conductor battery of the present invention through 300 mesh and use
Positive electrode.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 4.5 μm, specific surface area is
1.1m2/g.With ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows:
LiNi0.8Co0.1Mn0.1O2·0.05LiAlZrO4, lithium zirconium mixed oxide structural formula is (Li2O)0.5-(Al2O3)0.5-(ZrO3)。
Embodiment 11
14.8kg lithium carbonate is weighed to be added in 500L kneader, open stirring be added 70kg polyvinylpyrrolidone and
40kg deionized water adds 70.9kg strontium carbonate and 63.9kg zirconium hydroxide after stirring sufficiently.By material stirring 50min
After be then transferred in pallet and be put into baking oven in 120 DEG C of baking 1.5h, keep material moisture content content about 20% to obtain blocks of solid
Material 11.
120kg deionized water is added in kneader, after adding the dissolution completely of 1.2kg sodium carboxymethylcellulose, then plus
Enter 100kg nickel-cobalt lithium manganate cathode material (LiNi0.5Co0.2Mn0.3O2) stirring 20min after add 21.5kg solid material 11,
After mixing 30min, slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through appropriate air (oxygen content body
Product is than being 60%, gas input 100Nm3/ h), 900 DEG C of processing material 8h are warming up to, material is after cooling through ceramic ball mill
It crushes, and is sieved to obtain object fast ion conductor battery positive electrode of the present invention through 300 mesh.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 10.9 μm, specific surface area is
2.3m2/g.With ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows:
LiNi0.5Co0.2Mn0.3O2·0.04LiSrZrO4, lithium zirconium mixed oxide structural formula is (Li2O)0.5-(Sr2O3)0.5-(ZrO3)。
Embodiment 12
It weighs 39.74kg monohydrate lithium hydroxide to be added in 500L kneader, opens stirring and 70kg polyvinyl pyrrole is added
Alkanone and 90kg deionized water add five water zirconium nitrate of 109.28kg manganese carbonate and 322.3kg after stirring sufficiently.By object
It is then transferred in pallet and is put into baking oven in 120 DEG C of baking 1.5h after material stirring 50min, material moisture content content about 20% is kept to obtain
To blocks of solid material 12.
In kneader be added 110kg deionized water, add 1.4kg polyvinyl alcohol be heated to 80 DEG C dissolution completely after,
55.3kg solid material 12 is added after adding 100kg lithium cobaltate cathode material stirring 20min after cooling, after mixing 30min,
Slurry is poured into pallet to be put into drying box and dries to obtain solid block material in 105 DEG C/10h.
The material of above-mentioned drying is packed into ceramic alms bowl, using ventilation 24m roller kilns, is passed through appropriate air (300Nm3/
H), 960 DEG C of processing material 8h are warming up to, material is crushed through ceramic ball mill after cooling, and is sieved to obtain the present invention through 300 mesh
Object fast ion conductor battery positive electrode.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 17.3 μm, specific surface area is
0.3m2/g.With ICP to the structural formula for preparing material after the quantitative elementary analysis of positive electrode through accounting are as follows: LiCoO2·
0.095LiMnZrO4, lithium composite xoide structural formula is (Li2O)0.5-(Mn2O3)0.5-(ZrO3)4。
Comparative example 1
That is the positive pole material of lithium cobalt acid that uses of embodiment 1, the median (D of materialv50) it is 15.3 μm, specific surface area
For 1.2m2/g。
Comparative example 2
That is 2 positive-material lithium manganate of embodiment, the median (D of materialv50) it is 9.4 μm, specific surface area 1.5m2/g。
Comparative example 3
That is 4 anode material nickel cobalt aluminic acid lithium material of embodiment, the median (D of materialv50) it is 7.2 μm, specific surface area is
1.6m2/g。
Comparative example 4
Directly fast ion conducting material is directly mixed with embodiment 1 with cobalt acid lithium, the specific steps are as follows:
Solid material 1 prepared by Example 1 is packed into ceramic alms bowl, is passed through appropriate air (300Nm3/ h), using ventilation
24m roller kilns, being passed through oxygen-enriched air, (oxygen content volume ratio is 45%, gas input 400m3/ h), it is warming up to 650 DEG C of processing
Material 10h, material are crushed through cyclone vortex pulverizer after cooling, and humidity≤2% of surrounding air is controlled when crushing, and
It is sieved to obtain object lithium fast-ionic conductor material of the present invention through 300 mesh.Then in ratio and ontology cobalt acid lithium same as Example 1
Comparative example positive electrode is prepared in positive electrode physical mixed.
Obtain the median (D of material afterwards after tested using Malvern ParticleSizerv50) it is 15 μm, specific surface area is
0.9m2/g。
In 4 gained positive electrode of comparative example, fast ion conducting material is only simply mixed with basic positive electrode, does not wrap
Overlay on its surface.
Positive electrode prepared in the above embodiments is subjected to following characterizations:
1. scanning electron microscope sem figure
By above-described embodiment 1, embodiment 2, comparative example 1, the positive electrode powder that comparative example 2 is prepared swept respectively
Retouch Electronic Speculum SEM test, comparative example 1, comparative example 2, embodiment 1 and embodiment 2 scanning electron microscope (SEM) photograph be respectively Fig. 2-a (times magnification
Number Mag=3.00KX), Fig. 2-b (amplification factor Mag=5.00KX), Fig. 2-c (amplification factor Mag=3.00KX), Fig. 2-d (put
Big multiple Mag=5.00KX) result.
By Fig. 2-a, Fig. 2-c as it can be seen that one layer of nanoscale has uniformly been wrapped up on cobalt acid lithium surface (Fig. 2-c) after processing
Fast-ionic conductor, and have coating on size particles body.By Fig. 2-d as it can be seen that since lithium manganate particle surface is relatively more broken,
The surface of its angular particle also creates the fast-ionic conductor of the tufted of nanoscale size.And fast-ionic conductor is as far as possible
It is attached together with LiMn2O4 ontology.
It is detected with same method, other embodiments basis positive electrode surface has also coated fast-ionic conductor.
2, full battery preparation and Performance Evaluation
The positive electrode powder that above-described embodiment and comparative example are prepared is as a positive electrode active material by 354270 types
It is 1.4Ah or so flexible-packed battery that battery design, which is prepared into capacity, and preparation process is common process.Production full battery is mainly used
In investigation high temperature circulation and security impact.Wherein assessing applicable kind is 354270 flexible package square electric of winding-structure
Pond, the battery length of production are 35mm, width 42mm, with a thickness of 7mm.
Anode pole piece preparation is usually by preparing slurry, coating and cold pressing, and the techniques such as cutting are made, and effectively anode is living in pole piece
Property content of material be 97.5%, pole coating average weight be 0.0164g/cm3, pole coating width is 61mm, pole piece activity
The substance gross area is 463.6cm2, for Al foil substrate with a thickness of 14 μm, pole piece compaction density is calculated as 3.6g/cm with active material3。
The preparation method of negative electrode tab usually via slurry is prepared, is coated with, cold pressing, the processes preparation such as cutting.Using artificial stone
When ink is used as negative electrode active material, pole piece effective negative electrode active material (artificial graphite) content after preparation is 96.0%, pole piece
Coating weight is 0.0086g/cm2, pole coating width is 62mm, and the pole piece active material gross area is 483.6cm2, copper foil base material
With a thickness of 8 μm, pole piece compaction density is calculated as 1.65g/cm with active material3。
To be welded with the positive plate of aluminium pole ears, isolation film (for through nano aluminium oxide handle with a thickness of 16 μm of PP/PE/
PP composite isolated film), it is welded with negative electrode tab of nickel tab etc. and winds the preparation naked battery core of squarely in order, and naked battery core is put into
In the aluminum plastic film being punched and side packing (about 135 DEG C × 5s, 5~8mm of width) are carried out, then through 85 DEG C/16h vacuum baking
It infuses afterwards electrolyte (electrolyte: TC-E280,3.2g/ are only), encapsulation (is changed after standing in the chemical conversion machine chemical conversion of LIP-5AHB06 type high temperature
At 0~3.85V of voltage, 0.1C charge, 0.2C electric discharge, temperature 45 C ± 2 DEG C), then carry out heat-sealing 2 (about 135 DEG C × 5s, width 5
~8mm) and volume test (test voltage 3.0~4.2V, 0.2C, 0.5C), up-to-standard battery core is selected for subsequent performance
Assessment.
The lithium battery of the production of the positive electrode obtained by embodiment 1-12 is referred to as embodiment lithium battery 1-12, comparative example 1-
The lithium battery of 4 gained positive electrodes production is referred to as comparative example lithium battery 1-4.
3, EIS testing result
By it is prepared in the above embodiments partly fill lithium ion cell polar ear nickel sheet welding draw after, be linked into electrochemical operation
It stands and carries out electrochemical impedance spectroscopy test after standing 10min, test voltage stepping is 0.05V, frequency 5Hz, obtains table 4 and figure
Result shown in 3.
4 embodiment and comparative example lithium battery EIS testing result of table
Wherein, the electrochemistry of embodiment lithium battery 1, embodiment lithium battery 4, comparative example lithium battery 1 and comparative example lithium battery 3
Impedance spectra is as shown in figure 3, embodiment lithium battery 1, embodiment lithium battery 4, comparative example lithium battery 1 and comparative example lithium battery 3
Curve numberings are respectively 2-a, 2-c, 2-b, 2-d.
By table 4 and Fig. 3 as it can be seen that being sent out using the lithium battery electrochemical impedance spectroscopy of fast-ionic conductor positive electrode of the present invention preparation
Apparent variation is given birth to, either real part or imaginary part resistance becomes smaller.Usually in lithium battery positive-negative plate, positive plate it is interior
Hinder larger, often determine the internal resistance situation of whole lithium battery, using after fast ion conducting material in-situ preparation of the present invention to lithium
Ion battery overall impedance improves clearly, lithium ion battery lithium ion abjection/insertion speed is improved, to be conducive to
Promote the chemical property of lithium ion battery.
4, safe drift bolt test
By QC/T 743-2006, (electric road vehicle is stored the battery that above-described embodiment and comparative example are made with lithium ion
Battery) sting (nail diameter of phi 8mm, puncture speed are 20~25mm/s) is carried out, overcharge (constant-current charge to 200% rated capacity)
Test will test qualified every group of lithium battery electric core and take 2-3, and the constant temperature 2h under room temperature condition (23 DEG C ± 2 DEG C) then exists
It is discharged to 3.0V by 0.5C on LIP-10AHB06 type high temperature chemical conversion machine, discharge off stands 30s, and it is thick to take out battery core detection battery core
Indexs such as degree, internal resistance, then restocking by 0.5C charges to 4.2V again, then with 20mA low current CV to blanking voltage be 4.2V, weight
It is new to take out amount of batteries Thickness Measurement by Microwave, voltage and internal resistance are held, battery core is then stood 2 hours and is tested by standard, is obtained such as Fig. 4-
A, representative result shown in Fig. 4-b and table 5.
5 embodiment sting test result of table
Wherein, Fig. 4-a and Fig. 4-b is respectively that the needle thorn voltage of embodiment lithium battery 1 and comparative example lithium battery 1 and temperature rise become
Change curve.
By Fig. 4-a and Fig. 4-b as it can be seen that only 120 DEG C of the battery core heating of embodiment lithium battery 1, still has after drift bolt test
There is certain open-circuit voltage, shows that its stability is preferable, and comparative example lithium battery 1 is in addition to catching fire, the internal resistance of battery core changes
Acutely, considerably beyond the maximum range of K-type thermocouple, comparative example 4 is mixed into the actual temperature of battery core although with physical method
Roughly the same fast-ionic conductor, but do not see the effect of fast-ionic conductor, thus be also not achieved of the invention identical
Effect.
A specific embodiment of the invention is described above by embodiment, it will be understood by those skilled in the art that on
Literary embodiment is merely for the purpose of citing, it is not considered that limiting the protection scope of the present invention with this, those skilled in the art are not
It can be modified, change or replacement under the premise of disengaging spirit of that invention, still, according to various etc. made by the present invention
With variation, the range that the present invention is covered is still fallen within.
In conclusion positive electrode surface of the present invention forms the fast gas ions layer of stable uniform, anode can avoid
Material powder granule in later period use process is directly contacted with electrolyte, to be conducive to positive electrode in high voltage, length is followed
Use in ring system, while improving the security performance of lithium battery.Preparation method economically feasible of the present invention, operation letter
Single, effect is obvious, with good application prospect.
Claims (17)
1. a kind of anode material for lithium-ion batteries, which is characterized in that including basic material and fast-ionic conductor clad, the packet
Coating is selected from following any:
(1) lithium-titanium composite oxide, chemical formula are (Li2O)x-(MαO2)y-(TiO3)z, M element is selected from cobalt, zirconium, lanthanum, aluminium, strontium, manganese
Or the one or more of yttrium,
(2) lithium zirconium mixed oxide, chemical formula are (Li2O)x-(MαO2)y-(ZrO3)z, M element is selected from cobalt, titanium, lanthanum, aluminium, strontium, manganese
Or the one or more of yttrium,
(3) lithium phosphorus complex chemical compound, chemical formula are (Li2O)x-(MαO2)y-(PO4)z, M element be selected from cobalt, zirconium, titanium, lanthanum, aluminium, strontium,
The one or more of manganese or yttrium, and M includes at least the one or two of titanium or zirconium；
Wherein, 0.1≤x≤1.5,0.3≤α≤2.5,0 < y≤2.0,0.1≤z≤4；
The basic material be selected from cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, LiMn2O4, LiFePO 4, nickel ion doped or
One of lithium nickel cobalt dioxide is two or more.
2. positive electrode according to claim 1, wherein 0.1≤(2x+ α * y)/z≤5.0.
3. positive electrode according to claim 1 or claim 2, wherein the quality of the basic material and fast-ionic conductor clad
Than for (60-95): (5-40), it is preferred that the mass ratio of the basic material and fast-ionic conductor clad is (75-95): (5-
25)。
4. any one of -3 positive electrode according to claim 1, wherein the median (D of the positive electrodev50):2-25
μm。
5. the preparation method of anode material for lithium-ion batteries described in claim 1, which is characterized in that include the following steps:
(1) raw material comprising fast-ionic conductor clad each element and polyketone resinoid are subjected to mixed dissolution, are obtained after dry
Fast-ionic conductor precursor compound；
(2) composite drying: being configured to colloidal sol for deionized water and thickener, is uniformly mixed after fast-ionic conductor is added, then
Basic material is added, obtains mixture after dry；
(3) it is sintered: mixture obtained by step (2) being sintered at 650-1000 DEG C, obtains the positive electrode.
6. preparation method according to claim 5, wherein the raw material total amount comprising fast-ionic conductor clad each element
Mass ratio with polyketone resinoid is (1-15): 1.
7. according to the preparation method of claim 5 or 6, wherein in step (2), the quality of the deionized water and thickener
Than for 100:(0.2-4.0), preferably 100:(0.5-1.5).
8. according to any one of the claim 5-7 preparation method, wherein in step (2), the deionized water and fast ion are led
The mass ratio of body is 100:(5-100), preferably 100:(10-55).
9. according to any one of the claim 5-8 preparation method, wherein the thickener is selected from sodium carboxymethylcellulose, hydroxyl
The one or more of ethyl cellulose, hydroxypropyl cellulose or polyvinyl alcohol.
10. according to any one of the claim 5-9 preparation method comprising the original of fast-ionic conductor clad each element
Material is selected from oxide, hydroxide, carbonate, sulfate, nitrate, acetate or the phosphatic one or two of each element
More than.
11. according to any one of the claim 5-10 preparation method, wherein the polyketone resinoid is polyvinylpyrrolidine
Ketone.
12. according to any one of the claim 5-11 preparation method, wherein the temperature of drying process described in step (1) is
80-150℃。
13. according to any one of the claim 5-12 preparation method, wherein drying process temperature described in step (2) is
105-180℃。
14. according to any one of the claim 5-13 preparation method, wherein the sintering process needs to be passed through oxygen rich gas,
The volume content of oxygen is 45-99.9%, and the flow of oxygen rich gas is 5-500Nm3/h。
15. a kind of anode material for lithium-ion batteries, which is characterized in that be prepared by any one of claim 5-14 the method
It arrives.
16. a kind of lithium ion battery, which is characterized in that including any one of claim 1-4 or the claim 15 positive material
Material.
17. lithium ion battery described in any one of claim 1-4 or claim 15 positive electrode or claim 16 exists
The application of lithium electric energy source domain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074688.0A CN109888208A (en) | 2019-01-25 | 2019-01-25 | Anode material for lithium-ion batteries and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074688.0A CN109888208A (en) | 2019-01-25 | 2019-01-25 | Anode material for lithium-ion batteries and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109888208A true CN109888208A (en) | 2019-06-14 |
Family
ID=66926957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910074688.0A Pending CN109888208A (en) | 2019-01-25 | 2019-01-25 | Anode material for lithium-ion batteries and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109888208A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504433A (en) * | 2019-08-29 | 2019-11-26 | 杭州语茵科技有限公司 | A kind of lithium lanthanum-oxides coated lithium ion battery tertiary cathode material and its preparation method |
| CN111592052A (en) * | 2020-05-25 | 2020-08-28 | 蜂巢能源科技有限公司 | Lithium nickel manganese oxide composite material, preparation method thereof and lithium ion battery |
| CN111682187A (en) * | 2020-07-08 | 2020-09-18 | 清陶（昆山）能源发展有限公司 | Coated composite cathode material, preparation method and application thereof |
| CN111755698A (en) * | 2020-07-06 | 2020-10-09 | 上海汽车集团股份有限公司 | Oxide solid electrolyte coated positive electrode material and preparation method thereof |
| CN112186178A (en) * | 2019-07-04 | 2021-01-05 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery and positive electrode active material |
| CN112186177A (en) * | 2019-07-04 | 2021-01-05 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery and positive electrode active material |
| CN112563462A (en) * | 2019-09-25 | 2021-03-26 | 珠海冠宇电池股份有限公司 | High-voltage composite anode material and lithium ion battery containing same |
| CN112563565A (en) * | 2020-11-13 | 2021-03-26 | 上海空间电源研究所 | Preparation method of lithium-sodium ion mixed solid electrolyte and solid-state mixed battery |
| CN112736230A (en) * | 2020-12-30 | 2021-04-30 | 天目湖先进储能技术研究院有限公司 | High-voltage composite spinel-coated cathode material and preparation method thereof |
| WO2021089886A3 (en) * | 2020-09-07 | 2021-07-08 | Evonik Operations Gmbh | Synthesis of nanostructured lithium zirconium phosphate |
| CN113258073A (en) * | 2021-07-06 | 2021-08-13 | 湖南长远锂科股份有限公司 | Coating modified lithium ion battery anode material and preparation method thereof |
| CN113346066A (en) * | 2021-08-02 | 2021-09-03 | 湖南长远锂科股份有限公司 | Phosphate-coated lithium cobaltate positive electrode material and preparation method thereof |
| CN114005972A (en) * | 2021-10-22 | 2022-02-01 | 陕西红马科技有限公司 | LLTO/nano flaky lithium cobaltate composite cathode material and preparation method thereof |
| CN114335534A (en) * | 2021-12-16 | 2022-04-12 | 中国科学技术大学 | Lithium cobaltate positive electrode material coated and modified by zirconium lithium phosphate fast ion conductor and preparation method and application thereof |
| CN114883555A (en) * | 2022-06-09 | 2022-08-09 | 贵州高点科技有限公司 | Multiphase manganese material and preparation method thereof, positive plate and secondary battery |
| CN115231612A (en) * | 2022-09-20 | 2022-10-25 | 河北格力钛新能源有限公司 | Method for preparing modified lithium titanate composite material and modified lithium titanate composite material |
| CN115557544A (en) * | 2022-10-28 | 2023-01-03 | 安徽格派新能源有限公司 | Preparation method of high-capacity lithium nickel manganese oxide |
| WO2023082435A1 (en) * | 2021-11-09 | 2023-05-19 | 远景动力技术(江苏)有限公司 | Composite lithium nickel manganese oxide positive electrode material and preparation method therefor, and lithium ion battery positive electrode plate |
| CN114005972B (en) * | 2021-10-22 | 2024-06-07 | 陕西红马科技有限公司 | LLTO/nano flaky lithium cobalt oxide composite positive electrode material and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773763A (en) * | 2004-11-08 | 2006-05-17 | 深圳市比克电池有限公司 | Lithium ion secondary cell with nickel-base anode active material and producing method thereof |
| CN103165896A (en) * | 2011-12-13 | 2013-06-19 | 湖南省正源储能材料与器件研究所 | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification |
| KR20140029840A (en) * | 2012-08-30 | 2014-03-11 | 주식회사 엘지화학 | Anode for a cable-type secondary battery and cable-type secondary battery including the same |
| CN103825001A (en) * | 2014-01-14 | 2014-05-28 | 深圳市振华新材料股份有限公司 | High-safety cathode material of lithium ion secondary battery as well as preparation method and application thereof in battery manufacture |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
| CN106711412A (en) * | 2016-12-13 | 2017-05-24 | 北京理工大学 | Composite lithium-rich manganese-based cathode material and preparation method thereof |
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN108206277A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN108448055A (en) * | 2018-03-12 | 2018-08-24 | 中国科学院物理研究所 | Anode material for lithium-ion batteries and preparation method thereof |
| JP2018147555A (en) * | 2017-03-01 | 2018-09-20 | 太平洋セメント株式会社 | Positive electrode active material composite for lithium ion secondary battery, and method for manufacturing the same |
| CN108963202A (en) * | 2018-05-28 | 2018-12-07 | 天津国安盟固利新材料科技股份有限公司 | A kind of ternary layered positive electrode of high temperature modification and its preparation and application |
| CN109192956A (en) * | 2018-09-10 | 2019-01-11 | 中南大学 | Basic zirconium phosphate lithium fast-ionic conductor coats nickel cobalt lithium aluminate cathode material and preparation method |
-
2019
- 2019-01-25 CN CN201910074688.0A patent/CN109888208A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773763A (en) * | 2004-11-08 | 2006-05-17 | 深圳市比克电池有限公司 | Lithium ion secondary cell with nickel-base anode active material and producing method thereof |
| CN103165896A (en) * | 2011-12-13 | 2013-06-19 | 湖南省正源储能材料与器件研究所 | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification |
| KR20140029840A (en) * | 2012-08-30 | 2014-03-11 | 주식회사 엘지화학 | Anode for a cable-type secondary battery and cable-type secondary battery including the same |
| CN103825001A (en) * | 2014-01-14 | 2014-05-28 | 深圳市振华新材料股份有限公司 | High-safety cathode material of lithium ion secondary battery as well as preparation method and application thereof in battery manufacture |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
| CN106711412A (en) * | 2016-12-13 | 2017-05-24 | 北京理工大学 | Composite lithium-rich manganese-based cathode material and preparation method thereof |
| CN108206277A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| JP2018147555A (en) * | 2017-03-01 | 2018-09-20 | 太平洋セメント株式会社 | Positive electrode active material composite for lithium ion secondary battery, and method for manufacturing the same |
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN108448055A (en) * | 2018-03-12 | 2018-08-24 | 中国科学院物理研究所 | Anode material for lithium-ion batteries and preparation method thereof |
| CN108963202A (en) * | 2018-05-28 | 2018-12-07 | 天津国安盟固利新材料科技股份有限公司 | A kind of ternary layered positive electrode of high temperature modification and its preparation and application |
| CN109192956A (en) * | 2018-09-10 | 2019-01-11 | 中南大学 | Basic zirconium phosphate lithium fast-ionic conductor coats nickel cobalt lithium aluminate cathode material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 彭继明等: "表面活性剂对Li7La3Zr2O12包覆富锂锰基层状正极材料的影响", 《硅酸盐学报》 * |
| 彭继明等: "表面活性剂对Li7La3Zr2O12包覆富锂锰基层状正极材料的影响", 《硅酸盐学报》, vol. 44, no. 4, 8 March 2016 (2016-03-08), pages 493 - 497 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112186178A (en) * | 2019-07-04 | 2021-01-05 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery and positive electrode active material |
| CN112186177A (en) * | 2019-07-04 | 2021-01-05 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery and positive electrode active material |
| CN110504433A (en) * | 2019-08-29 | 2019-11-26 | 杭州语茵科技有限公司 | A kind of lithium lanthanum-oxides coated lithium ion battery tertiary cathode material and its preparation method |
| CN112563462A (en) * | 2019-09-25 | 2021-03-26 | 珠海冠宇电池股份有限公司 | High-voltage composite anode material and lithium ion battery containing same |
| CN111592052A (en) * | 2020-05-25 | 2020-08-28 | 蜂巢能源科技有限公司 | Lithium nickel manganese oxide composite material, preparation method thereof and lithium ion battery |
| CN111592052B (en) * | 2020-05-25 | 2022-04-12 | 蜂巢能源科技股份有限公司 | Lithium nickel manganese oxide composite material, preparation method thereof and lithium ion battery |
| CN111755698A (en) * | 2020-07-06 | 2020-10-09 | 上海汽车集团股份有限公司 | Oxide solid electrolyte coated positive electrode material and preparation method thereof |
| CN111682187B (en) * | 2020-07-08 | 2021-09-10 | 清陶（昆山）能源发展有限公司 | Coated composite cathode material, preparation method and application thereof |
| CN111682187A (en) * | 2020-07-08 | 2020-09-18 | 清陶（昆山）能源发展有限公司 | Coated composite cathode material, preparation method and application thereof |
| WO2021089886A3 (en) * | 2020-09-07 | 2021-07-08 | Evonik Operations Gmbh | Synthesis of nanostructured lithium zirconium phosphate |
| CN112563565A (en) * | 2020-11-13 | 2021-03-26 | 上海空间电源研究所 | Preparation method of lithium-sodium ion mixed solid electrolyte and solid-state mixed battery |
| CN112736230A (en) * | 2020-12-30 | 2021-04-30 | 天目湖先进储能技术研究院有限公司 | High-voltage composite spinel-coated cathode material and preparation method thereof |
| CN113258073B (en) * | 2021-07-06 | 2021-09-28 | 湖南长远锂科股份有限公司 | Coating modified lithium ion battery anode material and preparation method thereof |
| CN113258073A (en) * | 2021-07-06 | 2021-08-13 | 湖南长远锂科股份有限公司 | Coating modified lithium ion battery anode material and preparation method thereof |
| CN113346066A (en) * | 2021-08-02 | 2021-09-03 | 湖南长远锂科股份有限公司 | Phosphate-coated lithium cobaltate positive electrode material and preparation method thereof |
| CN114005972A (en) * | 2021-10-22 | 2022-02-01 | 陕西红马科技有限公司 | LLTO/nano flaky lithium cobaltate composite cathode material and preparation method thereof |
| CN114005972B (en) * | 2021-10-22 | 2024-06-07 | 陕西红马科技有限公司 | LLTO/nano flaky lithium cobalt oxide composite positive electrode material and preparation method thereof |
| WO2023082435A1 (en) * | 2021-11-09 | 2023-05-19 | 远景动力技术(江苏)有限公司 | Composite lithium nickel manganese oxide positive electrode material and preparation method therefor, and lithium ion battery positive electrode plate |
| CN114335534A (en) * | 2021-12-16 | 2022-04-12 | 中国科学技术大学 | Lithium cobaltate positive electrode material coated and modified by zirconium lithium phosphate fast ion conductor and preparation method and application thereof |
| CN114883555A (en) * | 2022-06-09 | 2022-08-09 | 贵州高点科技有限公司 | Multiphase manganese material and preparation method thereof, positive plate and secondary battery |
| CN114883555B (en) * | 2022-06-09 | 2024-01-30 | 贵州高点科技有限公司 | Multiphase manganese material, preparation method thereof, positive plate and secondary battery |
| CN115231612B (en) * | 2022-09-20 | 2023-02-03 | 河北格力钛新能源有限公司 | Method for preparing modified lithium titanate composite material and modified lithium titanate composite material |
| CN115231612A (en) * | 2022-09-20 | 2022-10-25 | 河北格力钛新能源有限公司 | Method for preparing modified lithium titanate composite material and modified lithium titanate composite material |
| CN115557544A (en) * | 2022-10-28 | 2023-01-03 | 安徽格派新能源有限公司 | Preparation method of high-capacity lithium nickel manganese oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109888208A (en) | Anode material for lithium-ion batteries and its preparation method and application | |
| CN105070888B (en) | Ternary material of CNT graphene complex three-dimensional network structure cladding of coupling and preparation method thereof | |
| CN107437619A (en) | A kind of anode for lithium battery material and preparation method thereof | |
| CN103794776B (en) | A kind of high voltage, high-pressure solid lithium ion battery composite cathode material and preparation method | |
| CN109950498A (en) | A kind of nickelic positive electrode and preparation method thereof with uniform clad | |
| CN103151528A (en) | Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material | |
| CN107394155A (en) | A kind of doping modification method of lithium cobalt oxide cathode material for lithium ion battery | |
| CN109888226A (en) | A kind of anode clad structure material and preparation method thereof with pinning effect | |
| CN105470482A (en) | Preparation method of aluminum-coated spherical lithium nickel cobalt aluminum oxide cathode material for lithium-ion battery | |
| CN105098158B (en) | A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping and preparation method thereof | |
| CN104835955A (en) | Nickel cobalt lithium manganate composite anode material of lithium ion battery and preparation method of nickel cobalt lithium manganate composite anode material | |
| CN108550802A (en) | A kind of nickel-cobalt-manganternary ternary anode material and preparation method that Y/La doping Co/B is coated altogether | |
| CN107994226A (en) | A kind of lithium-rich anode material of Mn adulterated lithium manganate and preparation method thereof | |
| CN107369815A (en) | A kind of lithium rechargeable battery composite positive pole and preparation method thereof | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN104681808A (en) | Method for preparing strontium salt doped lithium nickel manganese oxide cathode material of lithium ion battery | |
| Zhang et al. | Optimizing Li2O-2B2O3 coating layer on LiNi0. 8Co0. 1Mn0. 1O2 (NCM811) cathode material for high-performance lithium-ion batteries | |
| Zhang et al. | Synthesis and characterization of mono-dispersion LiNi0. 8Co0. 1Mn0. 1O2 micrometer particles for lithium-ion batteries | |
| Huang et al. | Surface modification of hierarchical Li1. 2Mn0. 56Ni0. 16Co0. 08O2 with melting impregnation method for lithium-ion batteries | |
| CN102163709B (en) | Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof | |
| CN102185163B (en) | Method for preparing inorganic aqueous solution lithium ion battery system by using monocrystal LiMnO (lithium manganese oxide) nanowire | |
| CN106784657A (en) | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material | |
| CN109742346A (en) | Si/Al coats nickel cobalt manganese anode material for lithium-ion batteries and preparation method thereof altogether | |
| CN113582253A (en) | Quaternary positive electrode material and preparation method and application thereof | |
| CN115611319B (en) | Copper-iron-manganese-based positive electrode material of sodium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |