CN109004195A - A kind of benefit lithium additive and preparation method thereof - Google Patents
A kind of benefit lithium additive and preparation method thereof Download PDFInfo
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- CN109004195A CN109004195A CN201810815263.6A CN201810815263A CN109004195A CN 109004195 A CN109004195 A CN 109004195A CN 201810815263 A CN201810815263 A CN 201810815263A CN 109004195 A CN109004195 A CN 109004195A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The invention discloses a kind of benefit lithium additives and preparation method thereof, and the lithium ion battery of lithium additive is mended containing this kind.Such benefit lithium additive is powder particle, and median particle diameter D50 is more than or equal to 0.1 μm and is less than or equal to 20 μm, chemical formula xLi2O·yM·zNaOb, wherein y > 0, z > 0,2x-y-z*a > 0.1, b > 0；M is Co, and one or more in Mn element, N Co's, Mn, Al, Ti is one or more.The benefit lithium additive is compared with lithium metal, organolithium, more stable, safety, when addition is in lithium ion battery, lithium source can be provided in initial charge, the consumption of lithium when to play compensation anode and cathode formation SEI film, discharge capacity, cycle performance and energy density for the first time are promoted, the lower cathode system of first charge-discharge efficiency is particularly suitable for.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, and in particular to a kind of benefit lithium additive and preparation method thereof.
Background technique
Lithium ion secondary battery has the advantages that high voltage, high-energy density, is widely used in consumer electronics product, storage
The power supply of energy system, dynamical system, the energy density for promoting lithium ion battery is that industrial circle and educational circles are concerned about the most all the time
The problem of.
During the initial charge of battery, positive and negative pole surface forms surface solid dielectric film (SEI film), can consume
Lithium to cause the loss of reversible lithium, reduces the irreversible carbonate for being cured to lithium of lithium or alkoxide, ester salt etc. for the first time
Efficiency reduces discharge capacity of the cell.Especially using the new type of negative active material of some high capacity (silicon, silicon alloy, silicon oxidation
Object or tin, tin alloy, tin-oxide etc.) when, the capacitance loss of initial charge process shows particularly evident.
To make up the lithium loss that initial charge forms SEI film, a kind of existing method of passage is in anode or cathode
Lithium additive is mended in pole piece addition.Such as application publication number is the patent document of CN102916164A and CN102916165A, is proposed
It is sprayed at positive and negative anodes pole piece respectively using the solution of organolithium as lithium additive is mended；In another example application publication number is
The patent document of CN1290209C proposes to be mixed together homogenate coating for lithium metal as benefit lithium additive and negative electrode material；Example again
It is equally that anode is added in lithium metal such as a kind of method that the patent document that application publication number is CN1830110A proposes prelithiation
Or negative electrode material, make the compensation lithium ion loss of positive and negative pole material prelithiation.
It can be seen that the prior art has mainly used two kinds of benefit lithium additives, one is lithium metal, another kind is organic
Lithium.When using lithium metal, the aridity of environment is required high, powdered lithium metal reactivity is very high, inflammable, Workflow
It splashes, it is difficult to manufacture processing, in inside battery it is possible that residual lithium metal, brings potential danger in subsequent use；Using organic
When lithium solution, it is dangerous to can avoid powder bring, but often activity is higher for organolithium, or even generally requires during being made
Processing can not be manufactured in air using inert atmosphere protection, while also very sensitive to moisture, be difficult to prior art simultaneous
Hold.
In many existing researchs, the oxide M O of section transitions metal (such as Mn, Fe, Co, Ni, Cu, Cr)xBy conduct
The potential application of the negative electrode material of lithium ion battery.Its principle of electrochemical reaction and the embedding lithium of the interlayer of graphite/de- lithium are different, also with
The alloying of the metals such as silicon, tin, zinc/no-alloyed process is different, and reaction principle is as follows: lithium insertion reaction MOx+2xLi→M+
xLi2O+xe-To lithium current potential generally between 0~2V；Lithium abjection reaction (i.e. back reaction) M+xLi2O+xe-→MOx+ 2xLi pairs
Lithium current potential is generally between 1~3V.Application publication number is that the patent document of CN107221650A proposes one using this principle
Kind can add the benefit lithium additive and preparation method thereof in anode, before preparation method is using lithium metal and transition metal oxide
Body is driven as raw material, chemical method lithium insertion reaction is utilized, it is subsequent to carry out surface oxidation treatment again.This benefit lithium additive is being made
When standby battery, avoid using lithium metal or organolithium, it is safer in the preparatory phase of battery, but still when preparing material
Lithium metal is used.Lithium metal is difficult to be prepared into micro mist, therefore, in the patent document that application publication number is CN107221650A
In synthesis process, the mixing of lithium metal and presoma can not accomplish the other mixing of micro-nano；Moreover, lithium metal turns in 180 degree
Liquid is turned to, lithium metal is very active in the molten state, it can react with various common crucible materials, such as quartz,
Corundum, ceramics, graphite etc. only use stainless steel crucible at present, and crucible life is shorter, and the feelings of corrosion leakage can occur quickly
Condition；Lithium metal raw material are more difficult to store, and cannot accomplish plug and play, the mixing of presoma powder and lithium metal need to be in argon gas
It is completed under protective atmosphere, practical operation and production have certain difficulty.
Summary of the invention
The purpose of the present invention is to provide a kind of benefit lithium additives and its synthetic method.
To achieve the above object, present invention provide the technical scheme that
A kind of benefit lithium additive, chemical component xLi2O·yM·zNaOb, wherein y > 0, z > 0,2x-y-z*a > 0.1, b >
0；M is Co, and one or more in Mn element, N Co's, Mn, Al, Ti is one or more.
It is mLi that the benefit lithium additive, which can be general formula,2O·ConMnp·CoqMnrOs·tTiO2Wherein 2m > n+p, n+p+q+
The material of r >=s, s >=4t.
It is cLi that the benefit lithium additive, which can be general formula,2O·dCo·eCoO·fAl2O3The material of wherein 2c > d, c >=4f.
In addition, the invention also discloses the preparation methods that this kind mends lithium additive, comprising:
(1) powder precursor containing M, N is prepared, wherein the element ratio of M, N and target product ratio are consistent；
(2) matched with the powder precursor containing M, N and Li salt (such as lithium carbonate, lithium hydroxide) according to target product chemistry
Than being matched and being sintered, the powder precursor containing Li, M, N is obtained；
(3) heating restores the powder precursor containing Li, M, N under reducing atmosphere；
(4) product of step (3) is subjected to one or more steps mixing with the gas containing oxygen and reacted, finally produced
Object.
The powder precursor containing M, N of step (1) can be the oxide containing M, N of coprecipitation method synthesis, hydroxide
Object, carbonate or more than several mixture, primary particle, offspring partial size, sphericity can be by being added speed, anti-
Answer the factor controllings such as kettle shape, temperature, pH value.
The powder precursor containing M, N of step (1) can also be oxide containing M, hydroxide, carbonate or more than it is several
The mixture of kind coats oxide, hydroxide, carbonate containing N on its surface
The sintering temperature of step (2) is preferably 400~1100 DEG C.
The reducing atmosphere of step (3) is preferably H2The Ar-H that volume content is 0.5~50%2Gaseous mixture, heating temperature are
100~700 DEG C.
The gas containing oxygen of step (4) can be dry air.
Compared with prior art, the beneficial effects of the present invention are:
First, preparation method is more simple and reliable: restoring the forerunner containing lithium and transistion metal compound with reducibility gas
Body prepares raw material without using lithium metal with gas-solid reaction instead of solid phase reaction, avoids corrosion of crucible and raw material storage
Security risk；
Second, the benefit lithium additive which is prepared has the utility model has the advantages that the benefit lithium additive and lithium metal, having
Machine lithium is compared, and more stable, safety can provide lithium source in initial charge, to play when adding in lithium ion battery
The consumption of lithium, promotes discharge capacity, cycle performance and energy density for the first time when compensation anode and cathode form SEI film, especially suitable
For the lower cathode system of first charge-discharge efficiency, such as: contain silicon, silicon alloy, Si oxide or tin, tin alloy, tin oxygen
The cathode system of compound.
Detailed description of the invention:
Fig. 1 is benefit lithium additive 3Li prepared by embodiment 12O·Co0.2Mn0.2·Co0.8Mn0.8O·0.05TiO2Scanning
Electromicroscopic photograph.
Fig. 2 is benefit lithium additive 3Li prepared by embodiment 22O·0.3Co·0.7CoO·0.2Al2O3Scanning electron microscope shine
Piece.
Fig. 3 is benefit lithium additive 3Li prepared by embodiment 32O·0.1Co·0.9CoO·0.1Al2O3Scanning electron microscope shine
Piece.
Specific embodiment
In order to which technical problem, technical solution and beneficial effect solved by the invention is more clearly understood, tie below
Accompanying drawings and embodiments are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
Mend lithium additive xLi2O·yM·zNaObSynthesis explanation:
Including following four step:
(1) powder precursor containing M, N is prepared, wherein the element ratio of M, N and target product ratio are consistent；
(2) matched with the powder precursor containing M, N and Li salt (such as lithium carbonate, lithium hydroxide) according to target product chemistry
Than being matched and being sintered, the powder precursor containing Li, M, N is obtained；
(3) heating restores the powder precursor containing Li, M, N under reducing atmosphere；
(4) product of step (3) is subjected to one or more steps mixing with the gas containing oxygen and reacted, finally produced
Object.
In some cases, step (1) and step (2) can merge.
Embodiment 1
According to CoMn (OH)2·0.05Ti(OH)4The molar ratio of metallic element is by cobaltous sulfate, manganese sulfate, sulfuric acid in chemical formula
Titanium is configured to the soluble metal mixed-salt aqueous solution that metal ion total concentration is 1.5mol/l；Compound concentration is 8mol/l simultaneously
Sodium hydroxide solution and concentration be 10mol/l ammonium hydroxide；The ammonium hydroxide that concentration is 10mol/l is added into reaction kettle and is used as reaction
Kettle base solution controls the ammonia concn in reaction kettle bottom liquid in 3.5g/l, and being then pumped into concentration by peristaltic pump is 8mol/l's
Sodium hydroxide solution adjusts pH in reaction kettle；Utilize the prepared soluble metal mixed-salt aqueous solution of peristaltic pump, sodium hydroxide
Solution, ammonium hydroxide cocurrent are added in reaction kettle and are stirred to react；Being stirred to react whole-process control temperature of reaction kettle is 40 DEG C, solvable
Property mixed metal saline solution feed rate control in 1.8l/h, the feed rate of ammonium hydroxide is controlled in 0.5l/h；Reaction process
The feed rate of middle control sodium hydroxide solution is to guarantee the pH value of reaction system as control standard；
Continuous feed 3 hours, subtract and stop alkali pump flow, continuously adds soluble mixed-salt aqueous solution and ammonium hydroxide is reacted,
The ammonia content that reaction system is improved by ammonia pump, makes ammonia content be increased to 4.5g/l, with the lasting progress of reaction feed, reaction
The fine grained of generation is gradually grown up, fine grained sphericity gradual perfection, surveys one with the every 2h of laser particle analyzer in reaction process
Secondary slurry granularity collects qualified material and goes forward side by side after detecting that second particle agglomerate particle size reaches target grain size D50 in reaction kettle
Row separation of solid and liquid, alkali cleaning, washing and dry screening.
By lithium carbonate and CoMn (OH)2·0.05Ti(OH)4It is uniform in high-speed mixer and mixing with the molar ratio of 6.06:1, so
It afterwards in oxygen atmosphere, is sintered 12 hours with 930 DEG C of temperature, by broken and screening, obtains the forerunner containing Li, Co, Mn, Ti
Body.By the presoma of Li, Co, Mn, Ti in H2The Ar-H that volume content is 12%2It is small with 430 DEG C of temperature sintering 7 under gaseous mixture
When；
After cooling, it is passed through dry air, and be sintered 2 hours at 130 DEG C, by broken and screening, obtains final product, it should
Mend lithium additive pattern as shown in Figure 1, D50 be 3.7 μm, obtain product 3Li2O·Co0.2Mn0.2·Co0.8Mn0.8O·
0.05TiO2Number is to mend lithium additive A.
Embodiment 2
Select D50 for 7 μm of cobalt oxide, lithium carbonate, aluminium hydroxide mix them according to the molar ratio of 1:6.06:0.4
After even, in 1100 DEG C of sintering 9h in air atmosphere；Once sintered product after the completion of sintering is obtained by crushing, removing iron, sieving
To the presoma of Li, Co, Al.
By the presoma of Li, Co, Al in H2The Ar-H that volume content is 5%2It is small with 500 DEG C of temperature sintering 6 under gaseous mixture
When；After cooling, it is passed through dry air, and be sintered 4 hours at 80 DEG C, by broken and screening, obtains final product, which adds
Add the pattern of agent as shown in Fig. 2, D50 be 7.1 μm, obtain product 3Li2O·0.3Co·0.7CoO·0.2Al2O3Number is benefit
Lithium additive B.
Embodiment 3
Aluminum sulfate is dissolved into cobalt sulfate solution, cobalt ions is configured to and aluminium ion concentration is respectively 90g/L and 18g/L
Mixed salt solution it is spare.A certain amount of pure water is injected as bottom liquid to reaction kettle, adds the ammonium bicarbonate soln tune pH value to be
8.5,40 DEG C are warming up to, it is under the mixing speed of 140rpm that cobalt aluminium mixing salt solution and concentration is molten for the ammonium hydrogen carbonate of 230g/L
Liquid is added in reaction kettle simultaneously occurs precipitation reaction, and charging process control reacting solution pH value is 8.0 or so, until material is grown
To 8 μm, charging is finished, and stops stirring, after solid-liquid layering, supernatant is taken away, vacating space continues to feed, and continues crystal
Grow to 7 μm.Slurry is dehydrated, obtains the precursor powder containing Co, Al after washing, drying, broken, screening.It will
Lithium carbonate and precursor powder containing Co, Al are uniform in high-speed mixer and mixing with the molar ratio of 6.06:1, then in oxygen atmosphere
In, it is sintered 12 hours with 1050 DEG C of temperature, by broken and screening, obtains the presoma containing Li, Co, Al.
By the presoma of Li, Co, Al in H2The Ar-H that volume content is 4%212 are sintered under gaseous mixture with 560 DEG C of temperature
Hour；After cooling, it is passed through dry air, and be sintered 3 hours at 170 DEG C, by broken and screening, obtains final product, the benefit
The pattern of lithium additive obtains product 3Li as shown in figure 3, D50 is 8.4 μm2O·0.1Co·0.9CoO·0.1Al2O3Number
To mend lithium addition of C.
Representative cells manufacturing instructions:
The preparation of anode pole piece: positive electrode active materials cobalt acid lithium (LCO), bonding agent Kynoar (PVDF) conductive agent
Super-P, the weight such as 96:2:2 of (or containing benefit lithium additive) as requested are added in N-Methyl pyrrolidone (NMP)
Anode sizing agent is made in stirring homogenate；By anode sizing agent double spread on plus plate current-collecting body, by drying, compacting, cutting, sanction
Anode pole piece is obtained after piece, soldering polar ear.
The preparation of cathode pole piece: negative electrode active material artificial graphite (or contain silicon, silicon alloy, silicon-carbon compound, silicon oxidation
Object or tin, tin alloy, tin-oxide), butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), weight as requested is such as
96:2:2 is added stirring homogenate in deionized water and negative electrode slurry is made；By negative electrode slurry double spread on negative current collector, warp
Cathode pole piece is obtained after crossing drying, compacting, cutting, cut-parts, soldering polar ear.
It should be understood that positive and negative anodes active material and ratio (as shown in table 1) have area in following comparative example and embodiment
Not, anode is added to and mends lithium additive in embodiment, and in addition to this, collector foil is identical, the unit area of anode pole piece
Coated weight it is identical, the coated length of positive and negative anodes pole piece is of same size, identical using electrolyte.
The preparation of electrolyte: select the lithium hexafluoro phosphate that concentration is 1M as lithium salts, with ethylene carbonate (EC): carbonic acid two
Ethyl ester (DEC): methyl ethyl carbonate (EMC), as solvent, additionally contains it assures that performance according to the weight ratio of 30:30:40
Additive.
The preparation of lithium ion battery: the cathode pole piece and anode pole piece that are prepared according to previous process and diaphragm are carried out
Assembling, be made battery battery core, battery battery core is fitted into outer packing, to it inside inject electrolyte after seal, progress preliminary filling, and
It is melted into and lithium ion secondary battery is made.
Test method explanation:
Volume test: at 25 ± 2 DEG C, with the electric current constant-current charge of 1500mA to 4.4V, then 4.4V constant-voltage charge extremely
Electric current is less than 60mA, obtains charging capacity, shelves 5 minutes, with 600mA electric current constant-current discharge to 3.0V, obtain discharge capacity.
Loop test: with the electric current constant-current charge of 1500mA to 4.4V, then it is less than in 4.4V constant-voltage charge to electric current
60mA, it shelves 5 minutes, with 1500mA electric current constant-current discharge to 3.0V, is recycled with this.400th capacity retention ratio=the
Discharge capacity × 100% of 400 discharge capacities/for the first time.
Energy density test: it at 25 ± 2 DEG C, with the electric current constant-current charge of 1500mA to 4.4V, then fills in 4.4V constant pressure
Electricity to electric current is less than 60mA, obtains charging capacity, shelves 5 minutes, with 600mA electric current constant-current discharge to 3.0V, obtains electric discharge energy
Amount.Battery energy density=discharge energy/(length × width x thickness)
Comparative example and embodiment explanation:
Illustrate: positive and negative anodes active material and ratio are had any different, in embodiment anode be added to mend lithium additive, except this with
Outside, collector foil is identical, and the coated weight of the unit area of anode pole piece is identical, the coated length width phase of positive and negative anodes pole piece
Together, identical using electrolyte.Each embodiment and comparative example make 50 batteries, and data are average value in table.
LCO is LiCoO2, SiCxFor silicon-carbon composite cathode material.
Battery comparative example and the production reference battery production of the battery of embodiment illustrate to make.
Analysis of experimental results:
Cell embodiments are compared with battery comparative example, it can be seen that it has used containing the battery for mending lithium additive A, B, C,
For promoting battery, discharge capacity, cycle performance and energy density all have beneficial effect for the first time.
According to above-mentioned principle, the present invention can also be made appropriate changes and modifications to the above embodiments.Therefore, this hair
The bright specific embodiment for being not limited to be explained above and describe should also be as some modifications and changes of the invention to fall into this
In the scope of protection of the claims of invention.In addition, although being used some specific terms in this specification, these terms
Merely for convenience of description, it does not limit the present invention in any way.
Claims (10)
1. a kind of preparation method for mending lithium additive, it is characterised in that: the chemical component of the benefit lithium additive is xLi2O·yM·
zNaOb, wherein y > 0, z > 0,2x-y-z*a > 0.1, b > 0；M is one or more in Co, Mn element, N Co, Mn, Al, Ti member
One of element is a variety of, and preparation method includes the following steps:
(1) powder precursor containing M, N is prepared, wherein the element ratio of M, N and target product ratio are consistent；
(2) it is matched and is sintered according to target product stoicheiometry with the powder precursor containing M, N and Li salt, contained
The powder precursor of Li, M, N；
(3) heating restores the powder precursor containing Li, M, N under reducing atmosphere；
(4) product of step (3) is subjected to one or more steps mixing with the gas containing oxygen and reacted, obtain final product.
2. preparation method according to claim 1, it is characterised in that: the powder precursor containing M, N of step (1) is coprecipitated
The oxide containing M, N of shallow lake method synthesis, hydroxide, carbonate or more than several mixture.
3. preparation method according to claim 1, it is characterised in that: the sintering temperature of step (2) is 400~1100 DEG C.
4. preparation method according to claim 1, it is characterised in that: the reducing atmosphere of step (3) is H2Volume content is
0.5~50% Ar-H2Gaseous mixture, heating temperature are 100~700 DEG C.
5. preparation method according to claim 1, it is characterised in that: the gas containing oxygen of step (4) is dry empty
Gas.
6. the benefit lithium additive of any one of Claims 1 to 5 the method preparation, it is characterized in that: the benefit lithium additive is powder
Particle, median particle diameter D50 are more than or equal to 0.1 μm and are less than or equal to 20 μm.
7. benefit lithium additive according to claim 6, it is characterised in that: the benefit lithium additive is mLi2O·ConMnp·
CoqMnrOs·tTiO2Wherein 2m > n+p, n+p+q+r >=s, s >=4t.
8. benefit lithium additive according to claim 6, it is characterised in that: the benefit lithium additive is cLi2O·dCo·
eCoO·fAl2O3Wherein 2c > d, c >=4f.
9. a kind of lithium ion secondary battery, it is characterised in that: contain and added using the described in any item benefit lithiums of claim 6~8
Agent.
10. lithium ion secondary battery according to claim 9, it is characterised in that: mend lithium additive and account for anode weight
Ratio be 0~15%, be free of 0%.
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| CN111370657A (en) * | 2018-12-26 | 2020-07-03 | 宁德时代新能源科技股份有限公司 | Positive electrode lithium supplement material and preparation method and application thereof |
| CN111640932A (en) * | 2020-06-03 | 2020-09-08 | 深圳市研一新材料有限责任公司 | High-purity positive electrode lithium supplement additive, preparation method thereof and lithium ion battery |
| CN113782706A (en) * | 2021-09-08 | 2021-12-10 | 远景动力技术(江苏)有限公司 | Lithium ion battery positive pole piece and preparation method and application thereof |
| CN114335428A (en) * | 2021-12-30 | 2022-04-12 | 重庆冠宇电池有限公司 | Positive plate, preparation method and battery |
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