CN109950616A - Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process - Google Patents
Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process Download PDFInfo
- Publication number
- CN109950616A CN109950616A CN201910190801.1A CN201910190801A CN109950616A CN 109950616 A CN109950616 A CN 109950616A CN 201910190801 A CN201910190801 A CN 201910190801A CN 109950616 A CN109950616 A CN 109950616A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- lacking oxygen
- sintering
- oxygen solid
- preparation process
- 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
Abstract
The present invention relates to field of lithium ion battery, a kind of Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process are disclosed.The preparation process of Lacking oxygen solid electrolyte includes: mixed raw material LiOH, La2O3、ZrO2, solvent, ball milling is added, drying obtains the first powder, is compacted the first powder, is placed under reducing atmosphere, is warming up to heat preservation sintering after the first sintering temperature, obtain once sintered object；Once sintered object is taken out, solvent, ball milling is added, drying obtains the second powder；It is compacted the second powder, is placed under reducing atmosphere, heat preservation sintering after the second sintering temperature higher than the first sintering temperature is warming up to, obtains double sintering object to get Lacking oxygen solid electrolyte, chemical formula Li7‑2xLa3Zr2O12‑x, reaction equation are as follows: 14LiOH+3La2O3+4ZrO2→2Li7‑2xLa3Zr2O12‑x+7H2O+2xLi2O。
Description
Technical field
The present invention relates to field of lithium ion battery, disclose a kind of Lacking oxygen solid electrolyte and its preparation process and comprising
The positive electrode of the Lacking oxygen solid electrolyte and positive plate and lithium ion battery comprising the positive electrode.
Background technique
In the past 20 years, it peters out with fossil energy and promotes people constantly to explore can to hold with getting worse for greenhouse effects
Continuous and clean energy resource.Lithium ion battery is as a kind of novel green high-energy battery, and because having, operating voltage is high, specific capacity is big, follows
The ring service life is long, self-discharge rate is low, memory-less effect and it is environmentally friendly the advantages that, attract the concern of numerous scientific research technical staff.
As energy density is constantly promoted, commercialized ternary material updates to NCM523, very from NCM333
Has the large-scale production of many producers to NCM622, NCM811.It is (usually said for layered lithium-nickel-based compound oxide
Ternary material) in the case where not changing charge cutoff voltage, increase one of the method that Ni content is its gram volume of raising, this is because
Ni2+/Ni3+It is oxidized to Ni3+/Ni4+Required current potential ratio Co3+It is transformed into Co4+It is lower.Ternary material (nickle cobalt lithium manganate) improves nickel
Content can greatly promote the specific capacity of material, therefore a kind of ideal material of nickelic ternary material necessarily large-sized battery in future
Material.
With the fast development of New-energy electric vehicle, using the solid-state of non-combustible solid electrolyte substitution organic electrolyte
Battery becomes and studies instantly because the features such as security risks such as leakage, on fire are able to achieve higher energy density is not present in it again
The next-generation battery technology of personnel's extensive concern.Even to this day, it has been found that many different crystal structures it is inorganic solid
State electrolyte includes metal oxide, sulfide, halide, nitride etc.；Relative to non-oxide species system, oxide solid-state
Electrolyte has better mechanical performance, chemistry and electrochemical stability (common electrochemical window > 5V), is used in solid-state
The generation that can effectively inhibit metal Li dendrite to pierce through in battery.
In oxide solid electrolyte of interest at present, carbuncle type Li7La3Zr2O12(LLZO) solid electrolyte material
Since Murugan in 2007 et al. report, it includes there are two types of crystal structure, high conductivity cubic phase (~10 for discovery-4S·
cm-1) and low conductivity tetragonal phase (~10-6S·cm-1).Researcher has done a large amount of doping experiment in succession, and (Li are mixed Al3+,
Fe3+, Ga3+；Zr are mixed Nb5+, Ta5+, Bi5+, Mo6+) carrying out stable cubic phase structure raising lithium electricity conductivity, these attempt big spininess
Modification to cation-bit, and negative oxygen ion stoichiometry is generally all defaulted as 12.Nearest researcher is in document
It is utilized in (Chem.Mater.2017,29,7189-7196)18O2Isotope exchange confirms in the system there are Lacking oxygen and to material
Material defect has a major impact, and the production of the Li ionic vacancies of corresponding proportion is also resulted according to the vacancy that electroneutral balances O anion
It is raw, and the Li ionic conductivity of LLZO material system and the content in the vacancy Li have close relationship.
Nickelic ternary LiNixCoyMn1-x-yO2The nickel content of (wherein 0.6 < x < 1,0 < y < 0.2) Yin Qigao, material exist
There are lithium/nickel mixing effects in charge and discharge process, while material surface ionic diffusion coefficient is low, cause material in proper order and times
Rate performance is bad.And be further used in solid state battery, due between tertiary cathode material and oxide solid electrolyte
Solid affixed touching, due to it can lead to anode-solid electrolyte interface separation because of multiple charge and discharge bring volume change, so that following
Interface resistance rapidly increases the serious problems for generating solid state battery failure after ring.
Summary of the invention
First first purpose of the embodiment of the present invention is to provide a kind of preparation process of Lacking oxygen solid electrolyte, apply
Lacking oxygen solid electrolyte ionic conducting property with higher made from the technical solution.
Second first purpose of the embodiment of the present invention is to provide a kind of Lacking oxygen solid electrolyte, it is with higher from
Subconductivity performance.
The third first purpose of the embodiment of the present invention is to provide a kind of positive electrode, by the positive electrode be applied to lithium from
Sub- battery, cycle performance sustainment rate with higher and lower internal resistance.
4th first purpose of the embodiment of the present invention is to provide a kind of lithium ion battery, cycle performance with higher
Sustainment rate and lower internal resistance.
In a first aspect, a kind of preparation process of Lacking oxygen solid electrolyte provided in an embodiment of the present invention, characterized in that packet
It includes:
Mixed raw material LiOH, La2O3、ZrO2, solvent, ball milling is added, drying obtains the first powder,
It is compacted first powder, is placed under reducing atmosphere, is warming up to after scheduled first sintering temperature described first
Heat preservation sintering is gone back under sintering temperature, obtains once sintered object；
The once sintered object is taken out, solvent, ball milling is added, drying obtains the second powder；
It is compacted second powder, is placed under the reducing atmosphere, is warming up to second higher than first sintering temperature
Heat preservation sintering is gone back under second sintering temperature after sintering temperature, obtains double sintering object to get Lacking oxygen solid electrolyte,
The chemical formula of the Lacking oxygen solid electrolyte are as follows: Li7-2xLa3Zr2O12-x, reaction equation are as follows: 14LiOH+3La2O3+
4ZrO2→2Li7-2xLa3Zr2O12-x+7H2O+2xLi2O。
Second aspect, the embodiment of the present invention provide a kind of Lacking oxygen solid electrolyte, are made using above-mentioned technique.
The third aspect, a kind of positive electrode provided in an embodiment of the present invention, including tertiary cathode material, the ternary just
Pole material is coated with above-mentioned Lacking oxygen solid electrolyte.
Fourth aspect, a kind of positive electrode provided in an embodiment of the present invention, including tertiary cathode material, the ternary just
Pole material is coated with Lacking oxygen solid electrolyte, the chemical formula of the Lacking oxygen solid electrolyte are as follows: Li7-2xLa3Zr2O12-x。
5th aspect, a kind of preparation method of positive electrode provided in an embodiment of the present invention, comprising:
Tertiary cathode material, Lacking oxygen solid electrolyte are taken, is uniformly mixed, ball milling scheduled duration obtains mixed powder, described
The chemical formula of Lacking oxygen solid electrolyte are as follows: Li7-2xLa3Zr2O12-x；
It is sintered the mixed powder under an inert atmosphere to get positive electrode, the Lacking oxygen solid electrolyte is coated on
Outside the tertiary cathode material.
6th aspect, a kind of positive electrode provided in an embodiment of the present invention are made using above-mentioned preparation method.
7th aspect, a kind of positive plate provided in an embodiment of the present invention, including plus plate current-collecting body,
It is coated with an at least positive electrode coating layer on an at least surface for the plus plate current-collecting body,
It include above-mentioned any positive electrode in each positive electrode coating layer.
Eighth aspect, a kind of lithium ion battery provided in an embodiment of the present invention, including above-mentioned any positive plate.
11. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
Second sintering temperature is 1150-1250 DEG C.
12. the preparation process of Lacking oxygen solid electrolyte according to claim 11, characterized in that
Second sintering temperature is 1200 DEG C.
13. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
After second sintering temperature lower heat preservation sintering when it is 3-9 hours a length of,
14. the preparation process of Lacking oxygen solid electrolyte according to claim 13, characterized in that
After second sintering temperature lower heat preservation sintering when it is 6 hours a length of,
15. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
It after each baking step, respectively further comprises: drying object is sieved；
First powder is the drying object after sieving；
Second powder is the drying object after sieving.
16. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
It is compacted first powder, specifically, first powder is compacted slabbing；
And/or second powder is specifically compacted slabbing by compacting second powder.
17. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
The solvent is isopropanol.
18. Lacking oxygen solid electrolyte made from a kind of any technique of claim 1 to 17.
19. a kind of positive electrode, comprising: tertiary cathode material, characterized in that be coated in the tertiary cathode material
Lacking oxygen solid electrolyte described in claim 18.
20. a kind of positive electrode, comprising: tertiary cathode material, characterized in that be coated in the tertiary cathode material
Lacking oxygen solid electrolyte, the chemical formula of the Lacking oxygen solid electrolyte are as follows: Li7-2xLa3Zr2O12-x。
21. positive electrode according to claim 20, characterized in that
The tertiary cathode material are as follows: LiaNixCoyMn1-x-yAzO2,
0.6,0 < y < 0.2 of 0.95 < a < 1.08, x >, x+y < 1,0≤z≤0.05, A Al, Ti, Mg, Zr are at least
It is a kind of.
22. positive electrode according to claim 21, characterized in that
The tertiary cathode material are as follows: LiNixCoyMn1-x-yO2,
X > 0.6,0 < y < 0.2, x+y < 1.
23. positive electrode according to claim 20, characterized in that
The mass percent of the tertiary cathode material and the Lacking oxygen solid electrolyte of cladding proportion are as follows:
The tertiary cathode material: 99.60-99.95wt%,
The Lacking oxygen solid electrolyte: 0.05-0.4wt%.
24. positive electrode according to claim 23, characterized in that
The mass percent of the tertiary cathode material and the Lacking oxygen solid electrolyte of cladding proportion are as follows:
The tertiary cathode material: 99.8wt%,
The Lacking oxygen solid electrolyte: 0.2wt%.
25. a kind of preparation method of positive electrode, characterized in that include:
Tertiary cathode material, Lacking oxygen solid electrolyte are taken, is uniformly mixed, ball milling scheduled duration obtains mixed powder, described
The chemical formula of Lacking oxygen solid electrolyte are as follows: Li7-2xLa3Zr2O12-x；
It is sintered the mixed powder under an inert atmosphere to get positive electrode, the Lacking oxygen solid electrolyte is coated on
Outside the tertiary cathode material.
26. the preparation method of positive electrode according to claim 25, characterized in that
It is sintered the mixed powder under an inert atmosphere, comprising:
The mixed powder is placed in sintering furnace, the inert atmosphere is passed through, is warming up to scheduled third sintering temperature,
It is sintered 4-6 hours also under the third sintering temperature, the third sintering temperature are as follows: 400-600 DEG C.
27. the preparation method of positive electrode according to claim 25, characterized in that
The chemical formula of the tertiary cathode material are as follows: LiaNixCoyMn1-x-yAzO2,
0.6,0 < y < 0.2 of 0.95 < a < 1.08, x >, x+y < 1,0≤z≤0.05, A Al, Ti, Mg, Zr are at least
It is a kind of.
28. the preparation method of positive electrode according to claim 27, characterized in that
The tertiary cathode material are as follows: LiNixCoyMn1-x-yO2,
X > 0.6,0 < y < 0.2, x+y < 1.
29. the preparation method of positive electrode according to claim 25, characterized in that
The mass percent of the tertiary cathode material and the Lacking oxygen solid electrolyte of cladding proportion are as follows:
The tertiary cathode material: 99.60-99.95wt%,
The Lacking oxygen solid electrolyte: 0.05-0.4wt%.
30. the preparation method of positive electrode according to claim 29, characterized in that
The mass percent of the tertiary cathode material and the Lacking oxygen solid electrolyte of cladding proportion are as follows:
The tertiary cathode material: 99.8wt%,
The Lacking oxygen solid electrolyte: 0.2wt%.
31. positive electrode made from a kind of any preparation method according to claim 25 to 30.
32. a kind of positive plate, including plus plate current-collecting body, characterized in that
It is coated with an at least positive electrode coating layer on an at least surface for the plus plate current-collecting body,
It include any positive electrode of claim 19 to 31 in each positive electrode coating layer.
33. positive plate according to claim 32, characterized in that
The positive electrode coating layer has been respectively coated on two surfaces of the plus plate current-collecting body.
34. positive plate according to claim 32, characterized in that
The mass percent of each component in each positive electrode coating layer is as follows:
Solid electrolyte: 10-40wt%；
The positive electrode: 50-80wt%；
Bonding agent: 3-5wt%；
Conductive agent: 2-4wt%.
35. positive plate according to claim 34, characterized in that
At least two positive electrode coating layers are coated on the surface of the plus plate current-collecting body,
From inside to outside from the plus plate current-collecting body:
The solid electrolyte content of the positive electrode coating layer of internal layer, the positive electrode lower than outer layer apply
The solid electrolyte content of layer of cloth；
The positive electrode content of the positive electrode coating layer of internal layer, the positive electrode higher than outer layer are coated with
The positive electrode content of layer.
36. positive plate according to claim 35, characterized in that
The two positive electrode coating layers are coated on the surface of the plus plate current-collecting body；
The mass percent of each component of the positive electrode coating layer of internal layer are as follows:
Solid electrolyte: 15wt%,
The positive electrode: 80wt%,
Bonding agent: 3wt%,
Conductive agent: 2wt%；
The mass percent of each component of the positive electrode coating layer of outer layer are as follows:
Solid electrolyte: 40wt%,
The positive electrode: 55wt%,
Bonding agent: 3wt%,
Conductive agent: 2wt%.
37. positive plate according to claim 32, characterized in that
The solid electrolyte is oxide or sulfide or Organic-inorganic composite solid electrolyte.
38. the positive plate according to claim 37, characterized in that
The oxide is Li7La3Zr2O12、Li0.5La0.5TiO3、Li1+xAlxTi2-x(PO4)3、Li1+xAlxGe2-x
(PO4)3It is any or at least two mixing.
39. the positive plate according to claim 38, characterized in that
The sulfide are as follows: 30Li2S·70P2S5、75Li2S-25P2S5、80Li2S-20P2S5、Li2S·SiS2、
Li7P3S11、Li11Si2PS12、Li9.54Si1.74P1.44S11.7Cl0.3、Li10MP2S12It is any or at least two mixing, wherein
M is any of Ge, Sn.
40. a kind of lithium ion battery, characterized in that any positive plate including claim 32 to 39.
Therefore it is had the advantages that using the present embodiment technical solution
1, the ionic conductance that Lacking oxygen helps to improve the solid electrolyte is generated by reducing atmosphere high temperature sintering LLZO
Rate；
2, by the Lacking oxygen-LLZO solid electrolyte be used to coat nickelic tertiary cathode material effectively raise its lithium from
Sub- diffusion coefficient improves cyclical stability of the nickelic positive electrode in charge and discharge process；
3, the NCM positive electrode after coating modification is used in solid state battery, solid state battery can be improved because of anode/solid-state
The solid affixed touching of electrolyte interface brings the problem of positive interface impedance increases in cyclic process；
4, the positive plate of multi-gradient coating can effectively improve solid state battery lithium ion in side of the positive electrode charge and discharge
Diffusion promotes the multiplying power and cyclical stability of solid state battery.
Detailed description of the invention
Fig. 1 is the clad structure schematic diagram that Lacking oxygen solid electrolyte provided by the invention coats tertiary cathode material；
Fig. 2 is that the front and back sides provided by the invention in plus plate current-collecting body are respectively arranged with symmetrical positive electrode coating layer
Coating structure schematic diagram.
Specific embodiment
Below in conjunction with specific attached drawing and embodiment, the present invention will be described in detail, herein illustrative examples of the invention
Attached drawing and explanation are used to explain the present invention, but not as a limitation of the invention.
The invention proposes a kind of preparation of Lacking oxygen solid electrolyte and its in the positive electrode side of lithium ion battery
The application in face.
The molecular formula of the present embodiment Lacking oxygen solid electrolyte is Li7-2xLa3Zr2O12-x, wherein 0 < x < 0.5.It is made
Standby technique is as follows:
(1) raw material is weighed.
According to stoichiometric ratio LiOH: La2O3: ZrO2=14: 3: 4, carries out raw material and weigh.
The present inventor has found in carrying out implementation process of the invention, wherein LiOH can be in above-mentioned stoichiometric ratio meter
Weight on the basis of, weighed by no more than 10% excessive amount, make actually the amount of weighing be greater than the weight that stoichiometric ratio meter obtains
Amount, weighs scheme using the excess, is conducive to the loss for avoiding subsequent high temperature sintering step lithium.
(2) mixed raw material is added solvent (can be, but not limited to as isopropanol), carries out high-energy ball milling 12 hours to scheduled
Granularity makes raw material carry out initial reaction in mechanical milling process, obtains a slurry, wherein drum's speed of rotation is set as 500r/
Min, zirconia ball abrading-ball.
(3) slurry is placed in ancient customs drying box and is dried, the powder of drying crosses 200 meshes, and powder after must sieving is denoted as
First powder.
(4) once sintered.
It is compacted the first powder, is placed in sintering utensil, is passed through reducing atmosphere, is gradually warming up to scheduled sintering temperature,
Once sintered object is growed when heat preservation sintering is scheduled under the sintering temperature, promotes raw material further anti-in high-temperature sintering process
It answers.
As the signal of the present embodiment, powder is preferably compacted slabbing by the present embodiment, is placed in Al2O3Crucible is sintered.
As the signal of the present embodiment, the reducing atmosphere of the present embodiment is in the gas that can be oxidized in air, such as: nitrogen
Any of gas, hydrogen, carbon monoxide, hydrogen sulfide, methane, sulfur monoxide, or (wherein hydrogen is few for the mixing of nitrogen and hydrogen
Amount), in the reducing atmosphere formed using mixed gas, water generation, the destruction to avoid moisture to agglomerated material should be avoided.
As the signal of the present embodiment, the present embodiment can be, but not limited to be warming up to 900 DEG C with the rate of 5 DEG C/Min,
Heat preservation sintering 4h under 900 DEG C of high temperature, obtains once sintered object.
(5) once sintered object is taken out, is added solvent (can be, but not limited to as isopropanol), is carried out high-energy ball milling 1 hour, it is former
Material further reacts in mechanical milling process, obtains secondary slurry.
Wherein, drum's speed of rotation is set as 500r/min, zirconia ball abrading-ball.
(6) secondary slurry is placed in ancient customs drying box and is dried, the powder of drying crosses 200 meshes, and powder after must sieving is denoted as
Second powder,
(7) double sintering.
It is compacted the second powder, is placed in sintering utensil, is passed through reducing atmosphere, is gradually warming up to scheduled sintering temperature
(1150-1250 DEG C any), the scheduled duration of heat preservation sintering (3-9 hours), obtain double sintering object under the sintering temperature.
As the signal of the present embodiment, powder compacting slabbing merging crucible is preferably sintered by the present embodiment.
As the signal of the present embodiment, the reducing atmosphere of the present embodiment be can be, but not limited to as N2Atmosphere or H2Atmosphere or two
The mixing of kind atmosphere.
As the signal of the present embodiment, the present embodiment can be, but not limited to be warming up to 1200 DEG C with the rate of 5 DEG C/Min,
The heat preservation sintering 6h under 1200 DEG C of high temperature, obtains double sintering object.
It so far is Lacking oxygen solid electrolyte to get the present embodiment: its molecular formula are as follows: Li7-2xLa3Zr2O12-x, 0 < x
< 0.5.
The present embodiment uses raw material Li OH, La2O3、ZrO2It applies example and adopts synthesis Li7-2xLa3Zr2O12-xChemical equation such as
Under:
14LiOH+3La2O3+4ZrO2→2Li7-2xLa3Zr2O12-x+7H2O+2xLi2O。
(8) ball milling double sintering object obtains the Lacking oxygen solid electrolyte powder of Ultra-fine, so as to subsequent applications.
Wherein, drum's speed of rotation is set as 500r/min, zirconia ball abrading-ball.
By the Lacking oxygen solid electrolyte Li of the present embodiment7-2xLa3Zr2O12-xIt is applied to tertiary cathode material, specifically:
(1) by Lacking oxygen solid electrolyte Li7-2xLa3Zr2O12-x, tertiary cathode material it is mixed by scheduled mass percent
Uniform mixture is closed, progress high-energy ball milling scheduled duration (being such as but not limited to 4 hours) in high energy ball mill is placed in, keeps oxygen empty
Position solid electrolyte Li7-2xLa3Zr2O12-xIt is evenly mixed in around tertiary cathode material.
As the signal of the present embodiment, which can be the common tertiary cathode material of the prior art, than
It such as can be, but not limited to as cobalt nickel lithium manganate ternary material: LiaNixCoyMn1-x-yAzO2, wherein 0.95 < a < 1.08, x >
0.6,0 < y < 0.2, x+y < 1,0≤z≤0.05, A are doped chemical, are such as but not limited to be at least the one of Al, Ti, Mg, Zr
Kind.
As the signal of the present embodiment, the cobalt nickel lithium manganate ternary material of selection can be with are as follows:
LiNixCoyMn1-x-yO2, wherein x > 0.6,0 < y < 0.2, x+y < 1.
As the signal of the present embodiment, the cobalt nickel lithium manganate ternary material of selection can be with specifically:
LiNi0.6Co0.2Mn0.2O2。
As the signal of the present embodiment, drum's speed of rotation is set as 500r/min, zirconia ball abrading-ball.
Wherein Lacking oxygen solid electrolyte Li7-2xLa3Zr2O12-xMass percent proportion in the mixture is 0.05-
0.4wt% (including end value), for example can be, but not limited in the present embodiment as 0.2wt%.
(2) after ball milling cross 200 meshes must sieve after powder, then powder after sieve is transferred to be connected with inert protective atmosphere (can
With but be not limited to Ar or N2Or two gas mixing) tube furnace in, be sintered 4-6h at a high temperature of at 400-600 DEG C
Afterwards, products therefrom is Lacking oxygen solid electrolyte Li7-2xLa3Zr2O12-xCoat the positive electrode of tertiary cathode material (also known as
Composite positive pole).
For example, the tertiary cathode material LiNi of the present embodiment0.6Co0.2Mn0.2O2To be reunited by multiple primary particles (monocrystalline)
The second particle spherical in shape formed, then Lacking oxygen solid electrolyte Li7-2xLa3Zr2O12-xIt is coated on the second particle of the spherical shape
Periphery, clad structure schematic diagram is shown in Figure 1, and 102 in Fig. 1 are spherical in shape two for the tertiary cathode material being wrapped by
Secondary particle, 101 be Lacking oxygen solid electrolyte clad.
Due to Lacking oxygen solid electrolyte Li7-2xLa3Zr2O12-xClad ionic conductivity with higher, using this reality
The diffusion of the anode of ternary lithium ion battery, the electrolyte lithium ion in charge and discharge process can be significantly improved by applying a technical solution
Coefficient, and then it is effectively improved the cyclical stability of ternary lithium ion battery.
As the signal of the present embodiment, Lacking oxygen solid electrolyte Li is coated with using the present embodiment7-2xLa3Zr2O12-x's
The technique that composite positive pole prepares lithium ion battery can be by the prior art, can also be real according to technique provided in this embodiment
It is existing.
The present embodiment is in order to improve the diffusions of lithium ion charge and discharge in positive plate, the technique that anode takes multistep to be coated with
It realizes, the solid electrolyte content of different coating layers is different, the specific process is as follows:
(1) low solid electrolyte content layer coating.
Raw material is weighed by following mass percent:
Solid electrolyte: 10-40wt%, being such as but not limited to the amount of weighing is 15wt%；
Lacking oxygen solid electrolyte Li7-2xLa3Zr2O12-xThe composite positive pole of cladding: 50-80wt%, such as but it is unlimited
In the amount of weighing be 80wt%；
Bonding agent: 3-5wt%, being such as but not limited to the amount of weighing is 3wt%；
Conductive agent: 2-4wt%, being such as but not limited to the amount of weighing is 2wt%.
Wherein, above value range includes end value.
Wherein, solid electrolyte can be, but not limited to as oxide solid electrolyte in the prior art, such as
Li7La3Zr2O12、Li0.5La0.5TiO3、Li1+xAlxTi2-x(PO4)3, Li1+xAlxGe2-x(PO4)3Deng.
Solid electrolyte can with but be not limited to sulfide solid electrolyte in the prior art, for example may include: with
The sulfide of lower glass ceramics class: 30Li2S·70P2S5、75Li2S-25P2S5、80Li2S-20P2S5、Li2S·SiS2、
Li7P3S11And the sulfide of following crystalline state: Li11Si2PS12、Li9.54Si1.74P1.44S11.7Cl0.3、Li10MP2S12(M be Ge or
Person Sn) etc..
In addition, solid electrolyte can with but be not limited to compound made of selecting Organic-inorganic composite in the prior art
Solid electrolyte.
Bonding agent can be, but not limited to select Kynoar (abbreviation PVDF).
Conductive agent can be, but not limited to select conductive carbon black (Super P, abbreviation SP), carbon nanotube (Carbon Nano
Tube, abbreviation CNT) any or mixing, mixing both preferably.
Solvent, which is added, in above-mentioned weighed raw material (can be, but not limited to select N-methyl pyrrolidones (1-Methyl-2-
Pyrrolidinone, abbreviation NMP) in, it is then uniformly mixed in de-airing mixer, obtains slurry, equably by slurry
Coating is on positive and negative two surface of plus plate current-collecting body (being such as but not limited to as aluminium foil), 80-100 DEG C of drying, obtains and is once coated with
Positive plate is coated with one layer of positive electrode coating layer on each surface of plus plate current-collecting body.
(2) high solid electrolyte content layer coating.
Technique and step (1) similarly, the difference is that the mass percent of the solid electrolyte in the raw material of this step contains
Amount is higher than the content in step (1).For example, when the mass percentage content of the solid electrolyte in step (1) is 15wt%, this
The mass percentage content of the solid electrolyte of step is greater than 15wt%, is such as but not limited to as 20wt%.
So far, two layers of positive electrode coating layer is obtained, wherein by except interior, the solid state electrolysis of outer layer positive electrode coating layer
The mass percentage content of matter is greater than the mass percentage content of the solid electrolyte of the positive electrode coating layer of internal layer.
It is signal with step (1), (2), can also further coats the positive electrode coating layer of more layers, what is obtained is compound
Positive plate, from plus plate current-collecting body, the quality hundred of the composite positive pole for being coated with Lacking oxygen solid electrolyte of innermost layer
Divide than content highest, solid electrolyte mass percentage content is minimum；It is outermost to be coated with answering for Lacking oxygen solid electrolyte
The mass percentage content for closing positive electrode is minimum, solid electrolyte mass percentage content highest, from the inside to the outside, each anode material
Expect that the mass percentage content of the composite positive pole for being coated with Lacking oxygen solid electrolyte of coating layer successively reduces, solid-state electricity
Solution matter mass percentage content successively improves.For example, setting currently available anode composite piece has n-layer positive electrode coating layer,
The mass percentage content of the composite positive pole for being coated with Lacking oxygen solid electrolyte of each layer is denoted as X (i), the solid-state of each layer
The mass percentage content of electrolyte is denoted as Y (i), then: X (n) < X (n-1) < ... < X (i) < X (i-1) < ... < X
(1), Y (n) > Y (n-1) > ... > Y (i) > Y (i-1) > ... > Y (1), wherein i be more than or equal to n it is any from
So number.
Fig. 2 is to be respectively arranged with the coating structure signal of symmetrical positive electrode coating layer in the front and back sides of plus plate current-collecting body
Figure, in Fig. 2, since the content of binder, conductive agent is smaller, therefore ignores and is not illustrated, wherein 105 indicate anode collection
Body, 103 are expressed as being coated with the composite positive pole particle of Lacking oxygen solid electrolyte, and 104 indicate solid electrolyte.
By resulting anode composite piece and solid electrolyte membrane, lithium anode by lamination heat pressing process, solid-state is formed
Lithium metal battery, concrete technology is referring to the prior art.
It should be noted that the present embodiment is using the anode composite for being coated with Lacking oxygen solid electrolyte of the present embodiment
Material prepare solid lithium ion battery for signal, it is not limited to this, the composite positive pole can with but be not limited to apply
In the lithium ion battery of liquid electrolyte, specific lithium ion preparation process may refer to the prior art, and this will not be repeated here.
The application is further described below with reference to example.It should be understood that these embodiments are merely to illustrate the application and do not have to
In limitation scope of the present application.In the following example, if used material and reagent can be from business ways without specified otherwise
Diameter purchase obtains.
Embodiment 1a:
(a) Lacking oxygen solid electrolyte powder is prepared:
(1) by LiOH, La2O3、ZrO2Raw material is weighed according to stoichiometric ratio 14: 3: 4, and wherein LiOH presses excess 10wt%
Excessive amount addition, to avoid the loss of lithium in high-temperature sintering process.
(2) raw material is mixed, obtains a slurry after high-energy ball milling 12h after addition solvent isopropanol, wherein ball mill turns
Speed is set as 500r/min, zirconia ball abrading-ball.
(3) slurry is placed in air dry oven and is dried, the powder of drying is compacted after crossing 200 meshes in flakes, by the pressure
Flaky powder after reality is placed in Al2O3In crucible, in reducing atmosphere (N2) in tube furnace, 900 are warming up to the rate of 5 DEG C/Min
DEG C, 900 DEG C of high temperature sintering 4h are kept, once sintered object is obtained；
(4) by once sintered object, isopropanol is added and is placed on high-energy ball milling 1h in ball mill, gained slurry is placed in air blast
200 meshes are crossed after drying in drying box and obtain powder, and wherein drum's speed of rotation is set as 500r/min, zirconia ball abrading-ball.
(5) it will be compacted be placed in Al in flakes after the powder drying in step (4)2O3In crucible, in reducing atmosphere (N2) tube furnace
In, 1100 DEG C are warming up to the rate in 5 DEG C/Min, continues to keep 1100 DEG C of high temperature sintering 6h, products therefrom is oxygen-containing sky
Position solid electrolyte Li7-2xLa3Zr2O12-xThe powder of (in 0 < x < 0.5).
Embodiment 2a
By sintering temperature changes into 1150 DEG C in step (5) in embodiment 1a.
Other are identical as embodiment 1a.
Embodiment 3a
By sintering temperature changes into 1200 DEG C in step (5) in embodiment 1a.
Other are identical as embodiment 1a.
Embodiment 4a
By sintering temperature changes into 1250 DEG C in step (5) in embodiment 1a, other are identical as embodiment 1a.
Embodiment 5a
By sintering temperature changes into 1200 DEG C in step (5) in embodiment 1a, when keeping the sintering of 1200 DEG C of high temperature sinterings
Between change into 4h.
Other are identical as embodiment 1a.
Embodiment 6a
By sintering temperature changes into 1200 DEG C in step (5) in embodiment 1a, when keeping the sintering of 1200 DEG C of high temperature sinterings
Between change into 8h.
Other are identical as embodiment 1a.
Embodiment 7a
Reducing atmosphere in step (3) in embodiment 1a, (5) is changed are as follows: the N that volume accounting is 96%2And volume accounts for
Than the H for 4%2Mixed-gas atmosphere；Sintering temperature changes into 1200 DEG C in step (5), keeps 1200 DEG C of high temperature sinterings
Sintering time changes into 6h.
Other are identical as embodiment 1a.
Embodiment 8a
Reducing atmosphere in step (3) in embodiment 1a, (5) is changed into CO；Sintering temperature changes into 1200 in step (5)
DEG C, keep the sintering time of 1200 DEG C of high temperature sinterings to change into 6h.
Other are identical as embodiment 1a.
Comparative example 1a
Reducing atmosphere in step (3) in embodiment 1a, (5) is changed into air atmosphere；Sintering temperature changes in step (5)
It is 1100 DEG C.
Other are identical as embodiment 1a.
Comparative example 2a
Reducing atmosphere in step (3) in embodiment 1a, (5) is changed into air atmosphere；Sintering temperature changes in step (5)
It is 1150 DEG C.
Other are identical as embodiment 1a.
Comparative example 3a
Reducing atmosphere in step (3) in embodiment 1a, (5) is changed into air atmosphere；Sintering temperature changes in step (5)
It is 1250 DEG C.
Other are identical as embodiment 1a.
Comparative example 4a
Reducing atmosphere in step (3) in embodiment 1a, (5) is changed into air atmosphere；Sintering temperature changes in step (5)
It is 1300 DEG C.
Other are identical as embodiment 1a.
Ionic conductivity measurement:
To embodiment 1a-8a, comparative example 1a-4a, after the sintering for the drying for taking each embodiment and comparative example to obtain respectively
Several grams of powder, be compressed into electrolyte sheet (circle) using powder compressing machine, with metal electrode form sandwich knot
Structure (ss/ Lacking oxygen LLZO/ss) measures, and blocking electrode uses stainless steel (stainless steel), abbreviation SS；It utilizes
Electrochemical workstation measures the conductivity at room temperature of electrolytic thin-membrane, obtains ionic conductivity contrast table shown in table one.
Wherein calculation formula is σ=d/ (RA), and d is the thickness of electrolyte sheet, and A is that electrolyte sheet connects with electrode
Effective area when touching；The corresponding numerical value of Z is all-in resistance R value when the-Z in impedance spectrum " is minimized.
The ionic conductivity contrast table of each product of table one
Therefore using the sintering process of embodiment 3a, there is intention not in terms of the ionic conductivity for improving material
The remarkable effect arrived.
It also further provides and a kind of applies the Lacking oxygen solid electrolyte of the present embodiment in solid lithium ion battery as follows
Embodiment.
Embodiment 1b
(a) cladding of positive electrode:
The Lacking oxygen solid electrolyte and tertiary cathode material LiNi that embodiment 3a is obtained0.6Co0.2Mn0.2O2With quality
Score 0.2wt%:99.8wt% is weighed, and is placed in high energy ball mill, and ball milling 4h is uniformly mixed, and drum's speed of rotation is set as
500r/min, zirconia ball abrading-ball.
The mixed powder obtained after ball milling crosses 200 meshes, is then transferred to powder and is connected with inert protective atmosphere (Ar)
In tube furnace, 400 DEG C are warming up to the rate in 5 DEG C/Min, 6h is sintered at 400 DEG C, products therefrom is Lacking oxygen solid-state
The LiNi of electrolyte cladding0.6Co0.2Mn0.2O2Material.
(b) low solid-state electrolyte layer coating:
By the LiNi after Lacking oxygen solid electrolyte cladding of 80wt%0.6Co0.2Mn0.2O2Material, 15wt%
Li7La3Zr2O12Solid electrolyte, 3wt% the CNT of SP, 1wt% of bonding agent PVDF, 1wt% be added in solvent NMP, stir
Mix uniformly mixed, obtained slurry is uniformly coated on the two sides with a thickness of the aluminium foil of 13um, 100 DEG C of drying.
(c) high solid-state electrolyte layer coating:
On step (b) positive plate obtained dried, it is then coated anode composite slurry, is only changed here:
Solid electrolyte Li in anode composite slurry7La3Zr2O12Mass fraction, 40wt% is increased to by 15wt%,
The mass fraction of corresponding anode drops to 55wt% from 80.
Other materials proportion and preparation process are constant.
(d) preparation of composite solid electrolyte film:
By polyacrylonitrile (polyacrylonitrile, abbreviation PAN) and bis- (trifluoromethanesulfonimide) lithiums (referred to as:
LiTFSI it) is dissolved in solvent anhydrous acetonitrile, polymeric matrix is made, wherein PAN: LiTFSI mass values 10: 1.
LLZO is added in polymeric matrix, with 200rpm revolution ball milling 4h, then by slurry cast in plate polytetrafluoro
On ethylene (Teflon), the composite solid for the 25um thickness that LLZO content is 8.5wt% is made in the dry 12h in argon filling glove box
Dielectric film.
(e) solid state battery assembles:
In glove box successively by anode composite piece, solid electrolyte membrane and the lithium anode of the gradient coating after roll-in
It is laminated, obtains all solid state soft-package battery after aluminum plastic film sealing, 85 DEG C of hot pressing；
Wherein lithium anode prepare it is as follows: metallic lithium powder and binder PVDF are dissolved in four with quality proportioning 90: 10
In hydrogen furans, mix slurry, be coated with, dry on copper foil, tabletting to get.
Embodiment 2b:
By Lacking oxygen solid electrolyte and LiNi in step (a) in embodiment 1b0.6Co0.2Mn0.2O2Mass fraction is than changing
Are as follows: 0.1wt%:99.9wt%.
Remaining is identical as embodiment 1b.
Embodiment 3b:
By Lacking oxygen solid electrolyte and LiNi in step (a) in embodiment 1b0.6Co0.2Mn0.2O2Mass fraction is than changing
Are as follows: 0.2wt%:99.8wt%.
Remaining is identical as embodiment 1b.
Embodiment 4b:
By Lacking oxygen solid electrolyte and LiNi in step (a) in embodiment 1b0.6Co0.2Mn0.2O2Mass fraction is than changing
Are as follows: 0.3wt%:99.7wt%.
Remaining is identical as embodiment 1b.
Embodiment 5b:
By Lacking oxygen solid electrolyte and LiNi in step (a) in embodiment 1b0.6Co0.2Mn0.2O2Mass fraction is than changing
Are as follows: 0.4wt%:99.6wt%.
Remaining is identical as embodiment 1b.
Embodiment 6b:
By Lacking oxygen solid electrolyte and LiNi in step (a) in embodiment 1b0.6Co0.2Mn0.2O2Mass fraction is than changing
Are as follows: 0.5wt%:99.5wt%.
Remaining is identical as embodiment 1b.
Embodiment 7b:
The high solid-state electrolyte layer coating step of step (c) in embodiment 1b is removed, once-combined anode is only carried out
Coating, remaining is identical as embodiment 1b.
Embodiment 8b:
By LiNi in step (a) in embodiment 3b0.6Co0.2Mn0.2O2It is changed to LiNi0.8Co0.1Mn0.1O2。
Remaining is identical as embodiment 3b.
Comparative example 1b:
Positive electrode LiNi0.6Co0.2Mn0.2O2The cladding process of Lacking oxygen solid electrolyte in embodiment 1b is not used, i.e.,
Without step (a).
Remaining is same as Example 1.
Comparative example 2b:
Positive electrode LiNi0.8Co0.1Mn0.1O2The cladding process of Lacking oxygen solid electrolyte in embodiment 8b is not used.
Remaining is identical as embodiment 8b.
Comparative example 3b:
(a) cladding of positive electrode:
Take butanol zirconium-butanol that mass fraction is 80wt% as zirconium oxide presoma；
Taking mass fraction is that the butanol zirconium of the positive electrode active materials NCM622 and 8wt% of 92wt% uniformly mixes, and is added to
It is stirred in ethyl alcohol, is dispersed with stirring by magnetic, mixing time 2h is evaporated at 80 DEG C, collects dry powder.Gained forerunner
Object carries out high temperature sintering (5h) in pure oxygen atmosphere at 800 DEG C after being fully ground, and gained final product is ZrO2Material institute
The NCM622 positive electrode of cladding.
Remaining is same as Example 1.
The cycle performance of all-solid-state battery, interface impedance test:
For embodiment 1b-7b and comparative example 1b-3b, under normal temperature conditions, solid state battery is carried out with 0.1C multiplying power and is filled
Electric loop test (charge cutoff voltage 4.2V, discharge cut-off voltage 3.0V)；Charging terminates when battery reaches and completely fills state every time,
The electrochemical alternate impedance spectrum figure EIS under the state is tested using electrochemical workstation, fitting obtains interface impedance, obtains table two
Shown in circulation conservation rate and interface impedance tables of data:
Table two: circulation conservation rate and the interface impedance table of comparisons
As shown in table two, no matter embodiment 3b is promoting circulation conservation rate or is all having meaning in terms of reducing interface impedance
To less than remarkable effect.
Therefore it is had the beneficial effect that using technical solution bring provided by the invention:
1, the ionic conductance that Lacking oxygen helps to improve the solid electrolyte is generated by reducing atmosphere high temperature sintering LLZO
Rate；
2, by the Lacking oxygen-LLZO solid electrolyte be used to coat nickelic tertiary cathode material effectively raise its lithium from
Sub- diffusion coefficient improves cyclical stability of the nickelic positive electrode in charge and discharge process；
3, the NCM positive electrode after coating modification is used in solid state battery, solid state battery can be improved because of anode/solid-state
The solid affixed touching of electrolyte interface brings the problem of positive interface impedance increases in cyclic process；
4, the positive plate of multi-gradient coating can effectively improve solid state battery lithium ion in side of the positive electrode charge and discharge
Diffusion promotes the multiplying power and cyclical stability of solid state battery.
Embodiments described above does not constitute the restriction to the technical solution protection scope.It is any in above-mentioned implementation
Made modifications, equivalent substitutions and improvements etc., should be included in the protection model of the technical solution within the spirit and principle of mode
Within enclosing.
Claims (9)
1. a kind of preparation process of Lacking oxygen solid electrolyte, characterized in that include:
Mixed raw material LiOH, La2O3、ZrO2, solvent, ball milling is added, drying obtains the first powder,
It is compacted first powder, is placed under reducing atmosphere, is warming up to after scheduled first sintering temperature in first sintering
At a temperature of go back heat preservation sintering, obtain once sintered object；
The once sintered object is taken out, solvent, ball milling is added, drying obtains the second powder；
It is compacted second powder, is placed under the reducing atmosphere, the second sintering higher than first sintering temperature is warming up to
Heat preservation sintering is gone back under second sintering temperature after temperature, obtains double sintering object to get Lacking oxygen solid electrolyte,
The chemical formula of the Lacking oxygen solid electrolyte are as follows: Li7-2xLa3Zr2O12-x, reaction equation are as follows: 14LiOH+3La2O3+4ZrO2
→2Li7-2xLa3Zr2O12-x+7H2O+2xLi2O。
2. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
The reducing atmosphere are as follows: nitrogen, hydrogen, carbon monoxide, hydrogen sulfide, methane, any of sulfur monoxide or nitrogen, hydrogen
The mixing of gas.
3. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
The actually amount of weighing of the raw material is at least equal to stoichiometrically LiOH: La2O3∶ZrO2=14: 3: 4 count weigh
Amount.
4. the preparation process of Lacking oxygen solid electrolyte according to claim 3, characterized in that
The actually amount of weighing of the LiOH relative to based on the stoichiometric ratio the amount of weighing it is excessive, excessive amount is less than or waits
In 10wt%.
5. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
First sintering temperature is 850-950 DEG C.
6. the preparation process of Lacking oxygen solid electrolyte according to claim 5, characterized in that
First sintering temperature is 900 DEG C.
7. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
After the first sintering temperature lower heat preservation sintering when it is 1-7 hours a length of.
8. the preparation process of Lacking oxygen solid electrolyte according to claim 7, characterized in that
After the first sintering temperature lower heat preservation sintering when it is 4 hours a length of.
9. the preparation process of Lacking oxygen solid electrolyte according to claim 1, characterized in that
It is warming up to the heating rate of first sintering temperature are as follows: 5 DEG C/Min；
And/or
It is warming up to the heating rate of second sintering temperature are as follows: 5 DEG C/Min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910190801.1A CN109950616A (en) | 2019-03-13 | 2019-03-13 | Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910190801.1A CN109950616A (en) | 2019-03-13 | 2019-03-13 | Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109950616A true CN109950616A (en) | 2019-06-28 |
Family
ID=67009714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910190801.1A Pending CN109950616A (en) | 2019-03-13 | 2019-03-13 | Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109950616A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111106380A (en) * | 2019-12-30 | 2020-05-05 | 华南师范大学 | Preparation method of solid electrolyte with surface coating and solid electrolyte battery |
| CN112563575A (en) * | 2020-12-08 | 2021-03-26 | 上海电力大学 | Composite solid electrolyte with transition molybdenum trioxide as filler, preparation method and application |
| CN112864353A (en) * | 2021-04-01 | 2021-05-28 | 清华大学深圳国际研究生院 | Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050252853A1 (en) * | 2004-05-13 | 2005-11-17 | Berland Brian S | Novel proton conducting materials and devices incorporating them |
| CN101009148A (en) * | 2007-01-26 | 2007-08-01 | 天津大学 | Compound lanthanum zirconate proton conductor mixed material and its preparing method |
| US20130230778A1 (en) * | 2012-03-02 | 2013-09-05 | Honda Motor Co., Ltd. | Lithium ion conductive composite electrolyte and lithium ion secondary battery using same |
| CN104813508A (en) * | 2012-05-23 | 2015-07-29 | 罗伯特·博世有限公司 | Process for producing an electrode for an electrochemical energy storage means and electrode |
| CN105428707A (en) * | 2015-11-24 | 2016-03-23 | 青岛能迅新能源科技有限公司 | Sintering method for reducing lithium ion loss of solid-state lithium ion electrolyte material Li7La3Zr2O12 |
| CN106784798A (en) * | 2017-02-15 | 2017-05-31 | 中国科学院过程工程研究所 | Positive electrode active materials, preparation method and high-performance anode sizing agent and all-solid lithium-ion battery comprising it |
| CN106898821A (en) * | 2017-03-16 | 2017-06-27 | 中国人民解放军63971部队 | A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method |
| WO2018075809A1 (en) * | 2016-10-21 | 2018-04-26 | Quantumscape Corporation | Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same |
| 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 |
| CN109004271A (en) * | 2018-08-01 | 2018-12-14 | 惠州亿纬锂能股份有限公司 | A kind of composite solid electrolyte film and its preparation method and application |
| CN109449414A (en) * | 2018-11-01 | 2019-03-08 | 江西中汽瑞华新能源科技有限公司 | A kind of anode composite material of lithium ion battery and the all-solid-state battery containing the material |
-
2019
- 2019-03-13 CN CN201910190801.1A patent/CN109950616A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050252853A1 (en) * | 2004-05-13 | 2005-11-17 | Berland Brian S | Novel proton conducting materials and devices incorporating them |
| CN101009148A (en) * | 2007-01-26 | 2007-08-01 | 天津大学 | Compound lanthanum zirconate proton conductor mixed material and its preparing method |
| US20130230778A1 (en) * | 2012-03-02 | 2013-09-05 | Honda Motor Co., Ltd. | Lithium ion conductive composite electrolyte and lithium ion secondary battery using same |
| CN104813508A (en) * | 2012-05-23 | 2015-07-29 | 罗伯特·博世有限公司 | Process for producing an electrode for an electrochemical energy storage means and electrode |
| CN105428707A (en) * | 2015-11-24 | 2016-03-23 | 青岛能迅新能源科技有限公司 | Sintering method for reducing lithium ion loss of solid-state lithium ion electrolyte material Li7La3Zr2O12 |
| WO2018075809A1 (en) * | 2016-10-21 | 2018-04-26 | Quantumscape Corporation | Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same |
| 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 |
| CN106784798A (en) * | 2017-02-15 | 2017-05-31 | 中国科学院过程工程研究所 | Positive electrode active materials, preparation method and high-performance anode sizing agent and all-solid lithium-ion battery comprising it |
| CN106898821A (en) * | 2017-03-16 | 2017-06-27 | 中国人民解放军63971部队 | A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method |
| CN109004271A (en) * | 2018-08-01 | 2018-12-14 | 惠州亿纬锂能股份有限公司 | A kind of composite solid electrolyte film and its preparation method and application |
| CN109449414A (en) * | 2018-11-01 | 2019-03-08 | 江西中汽瑞华新能源科技有限公司 | A kind of anode composite material of lithium ion battery and the all-solid-state battery containing the material |
Non-Patent Citations (3)
| Title |
|---|
| CHENG, L,ET AL.: "Enhanced lithium ion transport in garnet-type solid state electrolytes", 《JOURNAL OF ELECTROCERAMICS》 * |
| MARKUS KUBICEK,ET AL.: "Oxygen Vacancies in Fast Lithium-Ion Conducting Garnets", 《CHEMISTRY OF MATERIALS》 * |
| ZHAN, XIAOWEN,ET AL.: "Defect chemistry and electrical properties of garnet-type Li7La3Zr2O12", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111106380A (en) * | 2019-12-30 | 2020-05-05 | 华南师范大学 | Preparation method of solid electrolyte with surface coating and solid electrolyte battery |
| CN112563575A (en) * | 2020-12-08 | 2021-03-26 | 上海电力大学 | Composite solid electrolyte with transition molybdenum trioxide as filler, preparation method and application |
| CN112864353A (en) * | 2021-04-01 | 2021-05-28 | 清华大学深圳国际研究生院 | Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108847477B (en) | Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof | |
| CN109742365A (en) | A kind of sodium-ion battery positive material, preparation method and a kind of sodium-ion battery | |
| CN115207341B (en) | Preparation method of high-entropy oxide sodium ion battery positive electrode material | |
| CN1300872C (en) | Columnar structure LiCoO2 electrode material and its preparing process | |
| CN101847717A (en) | Preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries | |
| CN114229918B (en) | Method for regulating phase proportion in positive electrode material of sodium-ion battery, preparation and application thereof | |
| CN109950616A (en) | Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process | |
| Sun et al. | Sodium insertion cathode material Na0. 67 [Ni0. 4Co0. 2Mn0. 4] O2 with excellent electrochemical properties | |
| CN105810932B (en) | A kind of sodium-ion battery layered cathode material and preparation method thereof | |
| CN109167050A (en) | The production method of inexpensive 551530 type tertiary cathode material of high capacity | |
| CN111697204B (en) | Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof | |
| CN113764669A (en) | Layered oxide positive electrode material of high-voltage sodium-ion battery | |
| CN107579213A (en) | A kind of multiphase sodium ion battery electrode material structure design and performance control technique | |
| CN116119730A (en) | Oxide composite positive electrode material coated with borate in situ, preparation method and application | |
| CN115207340A (en) | Sodium ion battery layered oxide positive electrode material and preparation method and application thereof | |
| CN102709548A (en) | Multi-element cathode material for lithium ion battery and preparation method for multi-element cathode material | |
| CN113871702A (en) | Preparation of Geranite type solid electrolyte and all-solid-state battery application thereof | |
| CN115312735A (en) | Positive electrode material and preparation method and application thereof | |
| CN116425212A (en) | High-entropy doped layered oxide, preparation method thereof, positive electrode material and sodium ion battery | |
| Xue et al. | MgO-Coated Layered Cathode Oxide With Enhanced Stability for Sodium-Ion Batteries | |
| TW201912585A (en) | Preparation method and application of lithium-lithium nickel manganese oxide enriched cathode composite synthesizing the lithium-lithium nickel manganese oxide enriched cathode composite by using a solid phase method | |
| CN106252645A (en) | A kind of sodium-ion battery high nickel content ternary material and preparation method thereof | |
| CN103560245B (en) | The vanadium phosphate cathode material of graphene coated and its preparation method | |
| Li et al. | CuO/rGO nanocomposite as an anode material for high-performance lithium-ion batteries | |
| CN116826007A (en) | Layered positive electrode material of sodium ion battery and preparation method and application 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190628 |
|
| WD01 | Invention patent application deemed withdrawn after publication |