CN110120519A - The preparation method of the presoma of lithium-rich manganese-based anode material with stacking provisions and the lithium-rich manganese-based anode material with stacking provisions - Google Patents
The preparation method of the presoma of lithium-rich manganese-based anode material with stacking provisions and the lithium-rich manganese-based anode material with stacking provisions Download PDFInfo
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Abstract
The present invention relates to the presoma of the lithium-rich manganese-based anode material with stacking provisions and the preparation method of the lithium-rich manganese-based anode material with stacking provisions.The present invention constructs buffer system, uses the weak acid and mild base salts such as ammonium hydrogen carbonate or/and ammonium carbonate for precipitating reagent, complexing agent and pH adjusting agent, and preparation has the high-performance lithium-rich manganese-based anode material of stacking provisions under neutral or weak basic condition.Compare the preparation process of existing lithium-rich manganese-based anode material, method of the invention have synthesis condition is mild, simple process, foreign ion remaining less, the advantages such as adjustment parameter is few；On crystal structure, there are apparent stacking provisions；In performance, there is excellent high rate performance and cyclical stability, there are the potentiality that can carry out large-scale industrial production.
Description
Technical field
The invention belongs to the preparation of new energy materials and application fields, the in particular to system of anode material for lithium ion battery
Standby and application field relates more specifically to the presoma of the lithium-rich manganese-based anode material with stacking provisions and has stacking knot
The preparation method of the lithium-rich manganese-based anode material of structure, and as prepared by these methods with stacking provisions it is lithium-rich manganese-based just
Pole material and its application.
Background technique
With flourishing for electric car field, the following people are to the performance of lithium ion battery (such as mass/volume ratio
Energy, high rate performance, cyclical stability, safety and course continuation mileage etc.) propose increasingly higher demands.For example, to 2030
Year, the mass-energy density metric density of lithium ion battery is expected to reach the target of 500Wh/kg or more.In this process route
It leads down, the existing positive and negative electrode material electrochemical performance index of comprehensive analysis and related energy storage system technical maturity (such as lithium
Sulphur battery, lithium-air battery etc.) on the basis of, it is seen that: rich nickel ternary (NCM811) positive electrode, lithium-rich manganese-based anode material
Any combination collocation of material and high performance silicon-carbon cathode, lithium anode will be expected to obtain higher specific capacity, to reach
Target, and market can be met in the coming period of time to the performance requirement of lithium ion battery.Lithium ion battery just
In terms of the selection of pole material, compared to other existing positive electrodes, lithium-rich manganese-based anode material safety and thermal stability,
Average voltage, specific energy and cost etc. are even better.Therefore, lithium-rich manganese-based anode material is thought by academia and industrial circle
It is most rich prospect, next-generation power-type lithium ion battery and solid lithium battery positive electrode.
The crystal structure of lithium-rich manganese-based anode material is complex, and may be generally considered to be is by Li2MnO3And LiMO2(M
=Ni, Co, Mn) the layered superlattice solid solution that is constituted.Its specific energy and average voltage can be by regulating and controlling Li2MnO3With
LiMO2Relative proportions adjust.But the coulombic efficiency for the first time of this kind of positive electrode is lower (to be related to potential Li2MnO3-
MnO2Irreversible transition), high rate performance poor (electronics/lithium ion transmittability is poor), capacity and average voltage can be with following
Persistently rapid decay (irreversible transformation of rock salt/Spinel and the release of Lattice Oxygen occur) etc. of ring, these are insufficient
Through significantly limiting the extensive use of lithium-rich manganese-based anode material.
In order to solve or alleviate these problems, researcher has done a large amount of research work and trial.Most often adopt
Strategy is exactly to carry out bulk phase-doped or surface cladding etc..Can actually effectively it be inhibited by bulk phase-doped form
The release of oxygen in charging process, to achieve the effect that improve cyclical stability；Can actually effectively it be pressed down by surface cladding
The side reaction of electrode material surface processed and electrolyte, and then play the mesh for improving the cyclical stability of lithium-rich manganese-based electrode material
, but it is but and pessimistic to improve later effect.By meticulously analyzing it is not difficult to find that whether bulk phase-doped or surface
The defects of cladding, its crystal structure of used bulk material is all more regular, and stacking is not present structure, and Li2MnO3Phase
It is also relatively relatively low to content.It is not unique, but has its counterpart, and existing document shows that structure can be very big the defects of crystals introduce stacking
The chemical property of lithium-rich manganese-based anode material is promoted, performance is even better than certain bulk phase-doped, surface coated cases
Example.Therefore from the preparation of source presoma, by the design and optimization of preparation process, Effective Regulation material body it is microcosmic
Structure, and then this strategy for significantly promoting its chemical property will can yet be regarded as a good selection.But according to existing
Document report, lithium-rich manganese-based anode materials with good chemical property, with stacking provisions can only be by molten-salt growth method (such as
The molten-salt growth method or LiNO of KCl3The molten-salt growth method of/LiCl) it prepares, this is obviously unfavorable for industrialized large-scale production, greatly limits
The application of the lithium-rich manganese-based anode material with the category feature is made.
Non-patent literature 1, which is disclosed, has the lithium-rich manganese-based anode material of stacking provisions by molten-salt growth method preparation, and shows
Lithium-rich manganese-based anode material with stacking provisions can actually significantly improve its chemical property, but use fused salt legal system
It is standby, it is difficult to clean hidden danger there are fused salt, is unfavorable for further increasing the chemical property of battery.
Patent document 1 discloses a kind of hydrothermal modification method of lithium-rich manganese-based anode material comprising is closed using shallow lake method altogether
At the method for lithium-rich manganese-based anode material presoma, use sodium carbonate for precipitating reagent, ammonium hydroxide in the preparation method of the presoma
For complexing agent, reaction temperature is controlled at 40-80 DEG C.The preparation method needs to heat, and the process is more complicated (needs to control carbonic acid
The rate of the concentration and addition of sodium and ammonium hydroxide), the device is complicated.And stacking knot is not present in the lithium-rich manganese-based anode material prepared
Structure, there are room for improvement for chemical property.
Non-patent literature 1:Improving the electrochemical performance of layered
lithium-rich transition-metal oxides by controlling the structural defects,
Liu et.al,Energy&Environmental Science,2014,7,705-714。
Patent document 1:CN105655554B.
Summary of the invention
Problems to be solved by the invention
In view of the above-mentioned problems existing in the prior art, the purpose of the present invention is to provide a kind of completely new mode of thinking, lead to
Cross construction buffer system, use simplified coprecipitation prepare have the presoma of the lithium-rich manganese-based anode material of stacking provisions with
And the preparation method of the lithium-rich manganese-based anode material with stacking provisions.In addition, the purpose of the present invention is to provide by above-mentioned side
The presoma of lithium-rich manganese-based anode material prepared by method with stacking provisions and with stacking provisions it is lithium-rich manganese-based just
Pole material, and the lithium ion battery as prepared by the lithium-rich manganese-based anode material with stacking provisions.
The solution to the problem
A kind of preparation method of the presoma of the lithium-rich manganese-based anode material with stacking provisions, it is described that there are stacking provisions
Lithium-rich manganese-based anode material be expressed from the next:
(1-x)Li2MnO3·xLiMnyCozNitO2
Wherein, 0≤x≤1, y+z+t≤1
It the described method comprises the following steps:
(1) according to set stoichiometric ratio, manganese salt and cobalt salt and optional nickel salt is soluble in water, it is configured to mix
The solution A of metal salt；Weak acid and mild base salt is soluble in water, it is configured to solution B, the preferred NH of the weak acid and mild base salt4HCO3With/
Or (NH4)2CO3；
(2) in the case where the lasting stirring solution A, the solution B is at the uniform velocity added in the solution A, or
In the case where persistently stirring the solution B, the solution A is at the uniform velocity added in the solution B.During addition, only
The pH value of suspension obtained by being regulated and controled as the additional amount of the solution B or the solution A.Until the pH value of gained suspension
Between 7-8.5, preferably between 7-8, stop that the solution B or the solution A is added, continuing stirring to reaction terminates；
(3) by step (2) resulting reaction product, the rich lithium manganese with stacking provisions is can be obtained in process after post treatment
The carbonate precursor of base anode material.
The preparation method of the presoma of lithium-rich manganese-based anode material of the present invention with stacking provisions, wherein described
The concentration of the mixed metal salt of solution A be 0.02-5mol/L, preferably 0.1-3mol/L, more preferable 0.5-2.5mol/L, and/or
The concentration of the solution B is 0.02-5mol/L, preferably 0.5-2.5mol/L.
The preparation method of the presoma of lithium-rich manganese-based anode material of the present invention with stacking provisions, wherein step
(2) it is by speed that the solution B is added in the solution A or by the speed that the solution A is added in the solution B in
0.05-50mL/min, preferably 1-20mL/min.
The preparation method of the presoma of lithium-rich manganese-based anode material of the present invention with stacking provisions, wherein described
Postprocessing working procedures in step (3) include ageing, separation, washing and drying steps, it is preferable that digestion time 5-48h, it is more excellent
It is selected as 10-24h.
The preparation method of the presoma of lithium-rich manganese-based anode material of the present invention with stacking provisions, wherein described
Manganese salt described in step (1) is selected from one or more of manganese sulfate, manganese nitrate or manganese acetate, and the nickel salt is
Selected from one or more of nickel sulfate, nickel nitrate and nickel acetate, the cobalt salt is selected from cobaltous sulfate, cobalt nitrate or vinegar
One or more of sour cobalt.
The preparation method of the presoma of lithium-rich manganese-based anode material of the present invention with stacking provisions, wherein described
The presoma of lithium-rich manganese-based anode material with stacking provisions is the carbonate precursor with nanocluster microscopic appearance.
A kind of preparation method of the lithium-rich manganese-based anode material with stacking provisions, the rich lithium manganese with stacking provisions
Base anode material is expressed from the next:
(1-x)Li2MnO3·xLiMnyCozNitO2
Wherein, 0≤x≤1, y+z+t≤1
The described method includes:
It is prepared by the preparation method of the presoma of the lithium-rich manganese-based anode material according to the present invention with stacking provisions
The presoma of lithium-rich manganese-based anode material with stacking provisions；
The presoma of lithium-rich manganese-based anode material obtained with stacking provisions and lithium salts are mixed, by gained mixture
Pre-burning and secondary clacining are carried out in the heat treatment equipment for being connected with air or oxygen to get with the lithium-rich manganese-based of stacking provisions
Positive electrode.
The preparation method of lithium-rich manganese-based anode material according to the present invention, wherein the lithium salts be lithium carbonate and/or
Lithium hydroxide and/or the lithium salts excess 2-10wt%, preferably 3-10wt%.
The preparation method of lithium-rich manganese-based anode material according to the present invention with stacking provisions, wherein the pre-burning
Temperature control between 350-600 DEG C and/or the soaking time of the pre-burning is the temperature of 2-8h and/or the secondary clacining
Degree is 700-1000 DEG C and/or the soaking time of the secondary clacining is 5-20h.
The preparation method of lithium-rich manganese-based anode material according to the present invention with stacking provisions further comprises
Lithium-rich manganese-based anode material obtained with stacking provisions is subjected to gas displacement in atmosphere exchange system set in addition,
In inert gas, is sealed up for safekeeping in drying argon gas/nitrogen preferably without carbon dioxide, preferably contained in the atmosphere exchange system
There are gas absorption and dried reagent, the preferably described gas absorption and dried reagent are 3A/4A molecular sieve, sodium hydroxide and sodium carbonate
Deng.
The effect of invention
The present invention is by constructing a kind of buffer system, at room temperature only with such as NH4HCO3、(NH4)2CO3Equal weak acid and weak bases
Salt is precipitating reagent, complexing agent and acid-base modifier, and preparation has the high-performance of stacking provisions rich under neutral and weak basic condition
Lithium manganese-based anode material.The advantages of this method is, precursor preparation simple process, and preparation condition is mild (to be not required to heating and lazy
Property atmosphere protection), the microstructure of stoicheiometry and crystal need to can only carry out Effective Regulation by simple process, very suitable
For large-scale production.In addition, the electrochemical performances such as the average voltage of products therefrom, high rate performance, cyclical stability.
In addition, on the one hand can alleviate existing coprecipitation using method of the present invention and prepare lithium-rich manganese-based anode
(alkalinity as needed for precursor preparation is excessively high, and pH value is more demanding to the rotproofness of equipment higher than 8 for the deficiency of material；Chemical group
Divide and microscopic appearance is difficult to control, the consistency of product quality is relatively difficult to guarantee；It is difficult to prepare the heap with good chemical property
Pile structure；Used additive is mostly the combination such as sodium carbonate and ammonium hydroxide, and Control factors are more, and the device is complicated).On the other hand,
The technique that existing molten-salt growth method prepares stacking provisions lithium-rich manganese-based anode material can also be substituted, to overcome molten-salt growth method preparation process institute
Existing following defects: such as the more difficult washing of fused salt used, high rate performance is bad etc..Preparation method of the invention can both simplify work
Skill is conducive to large-scale production, and can obtain the high-performance lithium-rich manganese-based anode material with stacking provisions.
Detailed description of the invention
Fig. 1 shows using ammonium hydrogen carbonate or ammonium carbonate as precipitating reagent, complexing agent and pH adjusting agent (NHC) (embodiment 1), with
Sodium carbonate is precipitating reagent (NaC) (comparative example 1) and is precipitating reagent, ammonium hydroxide for complexing agent (NaHC) (comparative example 2) using sodium carbonate, adopts
The XRD spectrum of the presoma of the lithium-rich manganese-based anode material prepared by coprecipitation.
(a), (b), (c) in Fig. 2 respectively indicate comparative example 1 (NaC), comparative example 2 (NaHC) and embodiment 1 (NHC) institute
The SEM photograph of the lithium-rich manganese-based anode material presoma of preparation.
Fig. 3 indicates embodiment 1 (NHC), comparative example 1 (NaC) and comparative example 2 (NaHC), prepared lithium-rich manganese-based anode
The XRD spectrum and its Rivetld structure refinement figure of material.
(a), (b), (c) in Fig. 4 respectively indicate comparative example 1 (NaC), comparative example 2 (NaHC) and embodiment 1 (NHC), institute
The SEM photograph of the lithium-rich manganese-based anode material of preparation.
Fig. 5 expression uses ammonium hydrogen carbonate as precipitating reagent, complexing agent and pH adjusting agent (NHC) and uses comparative example 2 (NaHC),
The XRD spectrum (part) of obtained lithium-rich manganese-based anode material.
Fig. 6 indicates the specific volume of lithium-rich manganese-based anode material prepared by embodiment 1 (NHC) under the current density of 0.1C
Amount and the specific capacity of lithium-rich manganese-based anode material prepared by comparative example 2 (NaHC) compare.
Fig. 7 indicates the specific capacity of lithium-rich manganese-based anode material prepared by embodiment 1 (NHC) under the current density of 5C
Compare with the specific capacity of lithium-rich manganese-based anode material prepared by comparative example 2 (NaHC).
Fig. 8 shows richnesses prepared by lithium-rich manganese-based anode material prepared by embodiment 1 (NHC) and comparative example 2 (NaHC)
The high rate performance of lithium manganese-based anode material compares.
Specific embodiment
The present invention relates to: 1. lithium-rich manganese-based anode material presomas and preparation method thereof；2. lithium-rich manganese-based anode material and
Preparation method；3. the lithium ion battery prepared by lithium-rich manganese-based anode material.
The technical solution of above-mentioned 1-3 invention will be described in detail respectively below.Wherein in above-mentioned 1-3 invention, the richness lithium
Manganese-based anode material is expressed from the next:
(1-x)Li2MnO3·xLiMnyCozNitO2
Wherein, 0≤x≤1, y+z+t≤1
Preferably, the stoichiometric ratio of Mn, Co and Ni are at (0.54-0.95): (0.05-0.13): between (0-0.13) into
Row regulation.
1. the preparation method and its lithium-rich manganese-based anode material presoma of lithium-rich manganese-based anode material presoma
The preparation method of 1-1. lithium-rich manganese-based anode material presoma
The preparation method of above-mentioned lithium-rich manganese-based anode material presoma is under relatively mild conditions, by constructing buffer body
System, the method for preparing metal salt of weak acid using coprecipitation (under neutral or weak basic condition), the method includes following
Step:
(1) according to set stoichiometric ratio, manganese salt and cobalt salt and optional nickel salt is soluble in water, it is configured to mix
The solution A of metal salt；Weak acid and mild base salt is soluble in water, it is configured to solution B；
(2) in the case where the lasting stirring solution A, the solution B is at the uniform velocity added in the solution A, or
In the case where persistently stirring the solution B, the solution A is at the uniform velocity added in the solution B.During addition, only
The pH value of suspension obtained by being regulated and controled as the additional amount of the solution B or the solution A.Until the pH value of gained suspension
Between 7-8.5, stop that the solution B or the solution A is added, and continue stirring to reaction to terminate；
(3) by step (2) resulting reaction product, the carbon of lithium-rich manganese-based anode material is can be obtained in process after post treatment
Hydrochlorate presoma.
(preparation of aqueous solution of raw material)
It is according to set stoichiometric ratio, manganese salt and cobalt salt and optional nickel salt is soluble in water, it is configured to mixing gold
Belong to the solution A of salt.Type for preparing manganese salt, cobalt salt and optional nickel salt used in solution A is limited there is no special
It is fixed, as long as these salt can be dissolved in the water.These salt can be organic salt either inorganic salts, such as can be sulfuric acid
Salt, nitrate, acetate, hydrochloride etc. can be used selected from one of these salt or a variety of.Preferably, manganese salt is choosing
From one or more of manganese sulfate, manganese nitrate or manganese acetate, nickel salt is in nickel sulfate, nickel nitrate and nickel acetate
One or more, cobalt salt are selected from one or more of cobaltous sulfate, cobalt nitrate or cobalt acetate.From preventing halogen from causing
Pollution and cost from the viewpoint of when, more preferably use their sulfate.
Weak acid and mild base salt is soluble in water, it is configured to solution B.It is not special for the weak acid and mild base salt for preparing solution B
It limits, as long as it, which does not only pass through weak acid and mild base salt by other acid or alkali in the reaction, to control pH value between 7-8.5
, the preferably described weak acid and mild base salt is NH4HCO3And/or (NH4)2CO3。
For water used by solution A and solution B, there is no particular limitation, for example, can for deionized water, pure water or
Person/and distilled water, and preferably use deionized water.Solvent in solution A and solution B can be only water, can also not influence
Other solvents, such as ethyl alcohol etc. are added under the premise of the pH value of solution A and solution B.
The concentration of the mixed metal salt of solution A is 0.02-5mol/L.When solution A mixed metal salt concentration in 0.02-
When in the range of 5mol/L, it is not easy to form Spinel, and the crystallite dimension formed is more uniform, resulting sample can be with table
Reveal preferable high rate performance and cyclical stability.The presence of Spinel promotes rock salt structure to the irreversible of Spinel
Transformation, is unfavorable for the improvement of cyclical stability.And particle diameter distribution uniformity is poor, then the high rate performance of battery and cyclical stability be not
It is good.From the angle (such as high rate performance, cyclical stability) for further increasing chemical property, the mixed metal salt of solution A
Concentration preferred 0.1-3mol/L, more preferable 0.5-2.5mol/L, and can be 0.5mol/L, 0.6mol/L, 0.7mol/L,
0.8mol/L, 0.9mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L, 2.2mol/L,
2.5mol/L。
The concentration of solution B is 0.02-5mol/L.If the concentration of solution B is in the range of 0.02-5mol/L, it is not easy
Spinel, and the even grain size formed are formed, is conducive to carry out high current charge-discharge.From further increasing electrochemistry
The angle (such as high rate performance, cyclical stability) of performance, the preferred 0.5-2.5mol/L of the concentration of solution B, and can be
0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L,
1.8mol/L, 2.0mol/L, 2.2mol/L, 2.5mol/L.
(mixed processes)
In the case where the lasting stirring solution A, the solution B is at the uniform velocity added in the solution A, or is continued
In the case where stirring the solution B, the solution A is at the uniform velocity added in the solution B.During addition, only pass through
The additional amount of the solution B or the solution A come regulate and control gained suspension pH value.Until the pH value of gained suspension is in 7-
Between 8.5, preferably between 7-8, stop that the solution B or the solution A is added, continuing stirring to reaction terminates.Gained
The pH value of suspension can be 7.1,7.2,7.3,7.4,7.5,7.6,7.7,7.8,7.9,8.0,8.1,8.2,8.3,8.4.
From the angle of easily controllable mixed processes, preferably in the case where the lasting stirring solution A, by the solution B
It is at the uniform velocity added in the solution A.
The speed in the solution A is added in the solution B or the solution A is added employed in the solution B
Addition equipment there is no particular limitation, as long as be able to maintain be added speed be at the uniform velocity.Used addition equipment can example
For example microsyringe or peristaltic pump etc..It is not particularly limited for speed is added, but preferred 0.05-50mL/min.
When speed is added between 0.05-50mL/min, it is not easy to form Spinel, and the crystallite dimension formed is small and uniform, has
Conducive to the charge and discharge for carrying out high current.From the angle for improving efficiency and further increasing electric property, (high rate performance and circulation are steady
It is qualitative), more preferable 1-20mL/min, and can be 2mL/min, 3mL/min, 4mL/min, 5mL/min, 6mL/min, 8mL/
Min, 10mL/min, 12mL/min, 14mL/min, 16mL/min, 18mL/min.
In mixed processes, carry out that solution B or the solution A is added when being stirred, until gained suspension
PH value between 7-8.5 stops that solution B or the solution A is added, and continues stirring until reaction terminates.As the pH of suspension
It when value is between 7-8.5, is not easy to form Spinel, and the crystallite dimension formed is small and uniform, is conducive to progress high current and fills
Discharge performance.From the angle for further increasing electric property, more preferably between 7-8.The pH value of gained suspension can be
7.1,7.2,7.3,7.4,7.5,7.6,7.7,7.8,7.9,8.0,8.1,8.2,8.3,8.4.
(postprocessing working procedures)
Suspension obtained in mixed processes is post-processed, to obtain lithium-rich manganese-based anode material presoma.It is described
Postprocessing working procedures include ageing, separation, washing and drying steps.
Suspension obtained in mixed processes is stood to storage at room temperature to be aged, it is not special for digestion time
Restriction, but from improve preparation efficiency and improve chemical property angle, preferably digestion time be 5-48h, more preferably
10-24h。
Sediment is separated using conventional separation method.The separation method include but is not limited to be centrifugated,
Filtering etc..
After isolate is separated, the precipitating obtained by deionized water or pure water or distillation water washing
Object.
As a kind of example, if raw material uses sulfate, after sediment is separated and washs, using newly matching
The Ba of the 1mol/L of system2+Whether solution is identified remaining in cleaning solutionFiltering and washing alternately, when containing Ba2+'s
Without obvious Tyndall phenomenon or when white precipitate in cleaning solution, washing procedure terminates.
The sediment washed is dried, drying can spontaneously dry at room temperature, can also be with heat drying, it can also
To be freeze-drying.From the angle for improving efficiency and simplifying equipment, the vacuum drying oven or drum that are preferably 80-150 DEG C in temperature
It is dried in wind drying box, drying time 8-36h, preferably 10-15h.
1-2. lithium-rich manganese-based anode material presoma
It is mixed metal salt of weak acid, preferred mixed metal carbonic acid by lithium-rich manganese-based anode material presoma of the present invention
Salt.The mixed-metal carbonates are the carbonate precursor with nanocluster microscopic appearance.
2. the preparation method and lithium-rich manganese-based anode material of lithium-rich manganese-based anode material
The preparation method of 2-1. lithium-rich manganese-based anode material
The preparation method of lithium-rich manganese-based anode material presoma according to the present invention prepares lithium-rich manganese-based anode material
Presoma uniformly mixes lithium-rich manganese-based anode material presoma obtained and lithium salts, make gained mixture be connected with air or
Pre-burning and secondary clacining are carried out in the heat treatment equipment of person's oxygen to get lithium-rich manganese-based anode material.
(mixed processes)
Lithium-rich manganese-based anode material presoma and material mixing containing lithium are obtained into metal, lithium mixture.With excessive 2-
10wt%, preferably excess 3-10wt% mix substance containing lithium.Substance containing lithium used is not particularly limited, for example, being based on
The viewpoint being easy to get, preferably lithium hydroxide, lithium nitrate, lithium carbonate or their mixture.Especially, if holding from operation
From the point of view of Yi Du, quality stability, then more preferably using lithium hydroxide or lithium carbonate or their mixture.
There is no particular limitation for the mixed method of lithium-rich manganese-based anode material presoma and the substance containing lithium, and it is mixed that dry method can be used
Conjunction or wet-mixing.Dry mixed can be used common mixing machine such as ball mill or planetary mills etc. and be mixed, only
Lithium mixture is sufficiently mixed.But from the point of view of further increasing mixture homogeneity, preferred wet-mixing.Such as
Using ethyl alcohol etc. as dispersing agent, disperses lithium-rich manganese-based anode material presoma in dispersing agent with substance containing lithium and sufficiently stirred
It mixes, is then dried, to obtain well-mixed lithium mixture.
(pre-burning process)
Lithium mixture obtained in mixed processes is subjected to pre-burning, the purpose for carrying out pre-burning is the decomposition and richness of carbonate
The formation of lithium manganese-based anode material crystal grain, in favor of the acquisition of high-performance lithium-rich manganese-based anode material.The temperature control of pre-burning exists
Between 350-600 DEG C, preferably between 400-600 DEG C, the soaking time of pre-burning is 2-8h, preferably 4-7h.If by pre-burning temperature
Within the above range, complete release and the subsequent high-performance that can be conducive to carbon dioxide are lithium-rich manganese-based just for degree and burn-in time control
The acquisition of pole material.
(secondary clacining)
Substance obtained in pre-burning process is subjected to secondary clacining to obtain the good lithium-rich manganese-based anode material of crystallization degree
Material.The temperature of secondary clacining is 700-1000 DEG C, and preferably 700-900 DEG C, the soaking time of secondary clacining is 5-20h, preferably 10-
20h.When the temperature and time of secondary clacining within the above range when, the diffusion reaction speed of lithium is abundant, can be had
The lithium-rich manganese-based anode material of stacking provisions, and not will lead to abnormal grain growth, it is thus possible to obtaining has good electrification
Learn the positive electrode of performance.
(saving process)
When being saved lithium-rich manganese-based anode material according to a conventional method, carbon dioxide and water in air can be with rich lithiums
Slowly chemical reaction occurs for the surface of manganese-based anode material, forms carbonate on positive electrode surface, and then lead to positive material
Expect the deterioration of chemical property.Meanwhile the exposed time is longer, performance deterioration is more serious.In order to solve to deposit in the prior art
Lithium-rich manganese-based anode material the bad problem of preservation, the present inventor exists lithium-rich manganese-based anode material obtained
Gas displacement is carried out in atmosphere exchange system set in addition, environmental gas is replaced with into inert gas, is preferably replaced with without two
It is sealed up for safekeeping in drying argon gas/nitrogen of carbonoxide, gas absorption and dry examination is contained preferably in the atmosphere exchange system
Agent, the preferably described gas absorption and dried reagent are 3A/4A molecular sieve, sodium hydroxide and sodium carbonate.
It by such preservation process, solves problems of the prior art, can further keep prepared lithium
The chemical property of ion battery.
2-2. lithium-rich manganese-based anode material
Lithium-rich manganese-based anode material of the invention is expressed from the next:
(1-x)Li2MnO3·xLiMnyCozNitO2
Wherein, 0≤x≤1, y+z+t≤1
Preferably, the stoichiometric ratio of Mn, Co and Ni are at (0.54-0.95): (0.05-0.13): between (0-0.13) into
Row regulation.
Lithium-rich manganese-based anode material of the invention has stacking provisions, and average grain size circle is between 80-400nm.Shape
Looks are subsphaeroidal particles.Lithium-rich manganese-based anode material prepared by the present invention with stacking provisions has preferable high rate performance
And cyclical stability.
3. lithium ion battery
(anode)
Use above-mentioned lithium-rich manganese-based anode material as positive electrode active materials, makes the anode of lithium ion battery.Hereinafter, right
The example of the manufacturing method of anode is illustrated.Firstly, by above-mentioned lithium-rich manganese-based anode material, conductive material (Super P) and
Other conductive carbon based materials (such as graphene, Ketjen black), viscosity tune can also be added as needed in binder (PVDF) mixing
Whole dose etc., make anode sizing agent.
The mixing ratio of anode sizing agent can be adjusted according to particular use.Positive electrode, conductive material and binder
Mixing ratio can be set to it is same as the anode of well known lithium secondary battery, for example, by anode sizing agent in addition to the solvents
When the gross mass of solid component is set as 100 mass %, above-mentioned 60~95 mass % of lithium-rich manganese-based anode material, conduction can be contained
1~20 mass % of material, 1~20 mass % of binder.
Gained anode sizing agent is coated on to surface and the drying of the collector of such as aluminium foil, makes the anode of sheet.Root
It according to needs, in order to improve electrode density, also pressurizes sometimes through roll-in etc., it might even be possible to use carbon-coated aluminum foils.Such
To sheet anode can according to need cut etc. with become suitable size, for button, hard shell or flexible package
The production of equal batteries.But the method that positive production method is not limited to aforementioned exemplary, can also according to other methods into
Row.
As conductive material, the carbon based materials such as acetylene black, Ketjen black, graphene can be used for example.
Binder plays the role of fixed, connection active material particle, and polyvinylidene fluoride can be used for example in binder
(PVDF), polytetrafluoroethylene (PTFE) (PTFE), fluorubber, EP rubbers, styrene butadiene, cellulose-based resin, polyacrylic acid and
Sodium alginate etc..
As needed, make positive active material, conductive material and active carbon dispersion, dissolution is added in anode composite material
The solvent of binder.As solvent, specifically, the organic solvents such as n-methyl-2-pyrrolidone can be used.In addition, in order to
Increase Electric double-layer capacitor, active carbon can be added in anode composite material.
(cathode)
Lithium metal, lithium alloy etc. can be used in cathode.In addition, the cathode formed as follows can be used in cathode: can inhale
Hybrid adhesive in the negative electrode active material of deintercalate lithium ions is stored up, suitable solvent is added and forms negative electrode slurry, by what is obtained
Negative electrode slurry is coated on the surface of the metal foil current collectors such as copper and drying, according to need in order to improve electrode density compressed from
And form cathode.
As negative electrode active material, the organic compound of natural graphite, artificial graphite and phenolic resin etc. can be used for example
The coccoid of the object roasting carbonizable substances such as body and coke.Under above situation, as negative electrode binder, with anode likewise it is possible to make
N- methyl -2- pyrrolidines can be used as the solvent for dispersing these active materials and binder with fluorine resins such as PVDF
The organic solvents such as ketone.
(diaphragm)
Diaphragm is clamped between positive electrode and negative electrode and is configured.Diaphragm can be used for example for separating positive electrode and negative electrode
The thin film such as polyethylene, polypropylene and the film or fibreglass diaphragm with a large amount of small holes.
(non-aqueous electrolyte)
Non-aqueous electrolyte is to be dissolved in the lithium salts as supporting electrolyte obtained from organic solvent.As organic molten
Agent can be used alone cyclic annular selected from ethylene carbonate, propylene carbonate, butylene carbonate and trifluoromethy carbon vinyl acetate etc.
The linear carbonates such as carbonic ester and diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate and dipropyl carbonate and then tetrahydro
The sulphur compounds such as the ether compounds such as furans, 2- methyltetrahydrofuran and dimethoxy-ethane, ethyl-methyl sulfone, butyl sultone,
It a kind in phosphorus compounds such as triethyl phosphate, trioctyl phosphate etc. or is mixed with two or more.
As supporting electrolyte, LiPF can be used6、LiBF4、LiClO4、LiAsF6、LiN(CF3SO2)2And they
Complex salt etc..In turn, non-aqueous electrolyte may include the additives such as free radical scavenger, surfactant and fire retardant.
(solid electrolyte)
Existing traditional non-aqueous electrolyte can be replaced using organic or ceramic base solid electrolyte.When using solid-state
When electrolyte, diaphragm is not used.
(shape of battery is constituted)
By anode as described above, cathode, diaphragm and non-aqueous electrolyte constitutes or anode, cathode, solid state electrolysis
Texture at lithium ion battery of the invention the shapes such as cylindrical, square and button cell can be made.Using arbitrary shape
In the case of, make anode and cathode be laminated to form electrode body by diaphragm, non-aqueous electrolyte is made to be impregnated in the electrode obtained body, or
Anode and cathode by solid electrolyte be laminated constitute electrode body, with current collection lead etc. connection positive electrode collector be connected to outside
Positive terminal between and negative electrode collector be connected between external negative terminal, be enclosed within battery case, lithium ion be made
Battery.
Lithium ion battery prepared by the present invention has high specific discharge capacity, good cycling stability, different current densities
Under specific energy it is high.
Technical solution of the present invention will be further explained and described by embodiment and comparative example below.Under
Column embodiment only plays the role of explanation, is a part of the embodiments of the present invention, therefore cannot limit this with following embodiments
The protection scope of invention.
Embodiment 1:
[manufacture of lithium-rich manganese-based anode material presoma]
(1) under room temperature, with stoichiometric ratio 54:13:13, by MnSO4·H2O、NiSO4·6H2O and CoSO4·
7H2O is dissolved in deionized water, and being made into volume is 1L, and concentration is the mixed metal solion A of 2mol/L.By NH4HCO3It is dissolved in
In deionized water, it is made into the solution B of 2mol/L.
(2) microsyringe is utilized, solution B is added drop-wise in solution A with the speed of 5mL/min, is kept stirring, is only passed through
The pH value of the additional amount regulation gained suspension of solution B itself, stops being added dropwise when the pH to 8 of gained suspension, continues to stir
15h is mixed to react fully.
(3) after being aged 15h, gained precipitating is filtered, then filter cake is added in the deionized water of 5L and is washed
(being sufficiently stirred).So technique is filtered, washed alternately, until 1mol/LBaCl is added dropwise2After solution, filtrate is without white
Until precipitating or apparent Tyndall phenomenon.Finally, the qualified precipitating of washing is placed in 100 DEG C of vacuum oven dry
12h.Obtain the pink metal carbonate presoma with nanocluster microscopic appearance.
[analysis of lithium-rich manganese-based anode material presoma]
The presoma of the resulting lithium-rich manganese-based anode material of embodiment 1 is analyzed.The XRD diagram of NHC is denoted as in Fig. 1
Spectrum is the XRD spectrum of lithium-rich manganese-based anode material presoma prepared by embodiment 1.The test method of XRD is as follows: using graphite list
Color device, carries out θ -2 θ continuous scanning in the range of 2 θ are 10-120 °, and sweep speed is 2 °/min, tube current 200mA, pipe
Voltage is 45kV.
Be denoted as in Fig. 1 NHC XRD spectrum show the XRD diffracting spectrum of lithium-rich manganese-based anode material presoma with
MnCO3Standard spectrum (PDF#83-1763) correspond.
(c) in Fig. 2 shows the SEM photograph of the presoma of the lithium-rich manganese-based anode material of the preparation of embodiment 1.In Fig. 2
(c) display gained presoma is in nanoclusters tufted microscopic appearance.The average grain diameter of gained presoma primary particle is about 20nm.
[preparation of lithium-rich manganese-based anode material]
Wet grinding (solvent is ethyl alcohol) is used, by the Li of above-mentioned lithium manganese-based anode material presoma and excess 3wt%2CO3
Mixed, it is to be mixed uniformly after be put into the tube furnace for being connected with air, then the pre-burning 5h at 500 DEG C is forged at 850 DEG C again
15h is burnt, the heating rate being heat-treated twice is 2 DEG C/min to get the lithium-rich manganese-based anode material with stacking provisions.By institute
After the lithium-rich manganese-based anode material obtained carries out gas displacement in gas ventilator, sealed up for safekeeping with dry argon gas.
[analysis of lithium-rich manganese-based anode material]
The resulting lithium-rich manganese-based anode material of embodiment 1 is analyzed.
The XRD spectrum and its Rivetld structure refinement figure that NHC is denoted as in Fig. 3 are the preparation of embodiment 1 with stacking knot
The XRD spectrum and its Rivetld structure refinement figure of the lithium-rich manganese-based anode material of structure.The test method and condition of XRD and preceding institute
It states consistent.
The XRD spectrum that NHC is denoted as from Fig. 3 can be seen that in addition to showing stratiform α-NaFeO2(space group is structure) corresponding to characteristic diffraction peak except, had also appeared in the range of 2 θ=20-25 ° widthization, intensity is lower spreads out
Penetrate peak.The appearance of the diffraction maximum is exactly Li2MnO3Li and Mn is in the transition metal layer of (space group C2/m) with atomic ratio 1:2 shape
The result arranged at honeycomb.Crystallographic data shows that synthesized sample is Li2MnO3And LiMn1/3Co1/3Ni1/3O2Institute's group
At superlattices solid solution.Furthermore the peak intensity of diffraction maximum is weaker at 2 θ=20-25 °, and wideization degree is more obvious, and shows Li2MnO3Knot
The defects of structure is more, and stacking provisions are more obvious, therefore is consolidating with obvious stacking provisions by material synthesized by this technique
Solution.In addition, having carried out Rieveld structure refinement to XRD collected using Maud software, discovery is preferable quasi- in order to obtain
It closes as a result, must additionally increase the stack face defect model of a modulation during data fitting, and do not have to weak acid and weak base
The sample of salt does not have to then.Therefore in terms of testing with theory analysis two, can it prove using rich lithium manganese prepared by this technique
Base anode material has the fact that stacking provisions, rather than the inevitable outcome of coprecipitation method preparation.
(c) in Fig. 4 shows the SEM photograph of the lithium-rich manganese-based anode material of the preparation of embodiment 1.(c) in Fig. 4 shows institute
Obtain the subsphaeroidal particle that lithium-rich manganese-based anode material is average diameter about 200nm.
[production of lithium ion battery]
The production of anode pole piece
According to mass ratio 8:1:1, by obtained lithium-rich manganese-based anode material, conductive black Super P and binder
PVDF is dry-mixed, and dispersed/dissolved, magnetic agitation 6h, to prepare stream are then carried out in N- methyl-pyrrolidon (NMP) solvent
The dynamic good slurry of property.The slurry is equably cast on aluminium foil with applicator, is then done in 85 DEG C of air dry oven
Dry 12h.After drying, electrode slice is washed into the disk that diameter is 15mm.After weighing, the dry 6h in 120 DEG C of vacuum oven,
Finally move into the assembling that button cell (CR2032) is carried out in the glove box (water oxygen content is lower than 0.1ppm) full of argon gas.Activity
The load capacity of material lithium-rich manganese-based anode material is controlled in about 5mg/cm2。
The assembling of button cell
Using metal lithium sheet as cathode, with microporous polypropylene membrane (celgard2500) for diaphragm, with the LiPF of 1mol/L6-
The organic solution of EC/DEC (volume ratio of EC and DEC are 1:1) is electrolyte, and the assembling of button cell is assembled in glove box.
The evaluation of button cell chemical property
Constant current charge-discharge (in the voltage range of 2-4.8V), forthright again is carried out using LAND CT2001 battery test system
The test of the chemical properties such as energy and cyclical stability.It was found that at room temperature, when current density is 0.1C (1C=250mAh/g),
Its specific capacity is about 260mAh/g, and coulombic efficiency is about 71% for the first time.The specific capacity of 5C is about 150mAh/g.The specific capacity of 1C is about
For 240mAh/g, capacity retention ratio is about 80% after recycling 100 times, about 190mAh/g,.
Embodiment 2:
[manufacture of lithium-rich manganese-based anode material presoma]
(1) under room temperature, with stoichiometric ratio 54:11:3, by Mn (NO3)2·4H2O、Ni(NO3)2·6H2O and
CoSO4·7H2O is dissolved in deionized water, is made into the mixed ion solutions A of 1mol/L.By (NH4)2CO3It is dissolved in deionized water,
It is made into the solution B of 0.5mol/L.
(2) microsyringe is utilized, solution B is added drop-wise in solution A with the speed of 10mL/min, is kept stirring, is passed through
The pH value of the additional amount regulation gained suspension of solution B itself, stops being added dropwise when the pH to 7.5 of gained suspension, continue
15h is stirred to react fully.
(3) after being aged 15h, gained precipitating is filtered, then the deionized water that 5L is added in filter cake is washed and (is filled
Divide stirring).So it is filtered, washed technique alternately, the BaCl until 1mol/L is added dropwise2After solution, filtrate is without white
Until precipitating or Tyndall phenomenon.The qualified precipitating of washing is finally placed in 100 DEG C of vacuum oven dry 12h.I.e.
Obtain the pink metal carbonate presoma with nanocluster microscopic appearance.
[analysis of lithium-rich manganese-based anode material presoma]
Analysis (XRD spectrum same as Example 1 is carried out to the resulting lithium-rich manganese-based anode material presoma of embodiment 2
And SEM is not shown out, it is as a result similar to Example 1).Analysis the result shows that, the X-ray of lithium-rich manganese-based anode material presoma is spread out
Penetrate map and MnCO3Standard spectrum (PDF#83-1763) correspond.By sem analysis same as Example 1 (with implementation
Example 1 is similar), gained presoma is nanoclusters tufted, and the average grain diameter of the primary particle of gained presoma is about 20nm.
[manufacture of lithium-rich manganese-based anode material]
Wet grinding (solvent is ethyl alcohol) is used, by the Li of above-mentioned lithium manganese-based anode material presoma and excess 5wt%2CO3
Mixed, it is to be mixed uniformly after be put into the tube furnace for being connected with air, then the pre-burning 6h at 400 DEG C is forged at 900 DEG C again
10h is burnt, the heating rate being heat-treated twice is 2 DEG C/min to get the lithium-rich manganese-based anode material with stacking provisions.By institute
After the lithium-rich manganese-based anode material obtained carries out gas displacement in gas ventilator, sealed up for safekeeping with dry argon gas.
[analysis of lithium-rich manganese-based anode material]
Analysis same as Example 1 is carried out to the resulting lithium-rich manganese-based anode material of embodiment 2.Analysis the result shows that,
It is the solid solution with stacking provisions by material synthesized by this technique.Gained lithium-rich manganese-based anode material be average diameter about
The subsphaeroidal particle of 400nm.
[production of lithium ion battery]
The lithium ion battery of embodiment 2 is made by the way of same as Example 1, and using same as Example 1
Mode carries out the evaluation of chemical property with battery.The result shows that the specific capacity of 0.1C is about 250mAh/g, the specific capacity of 1C is about
For 240mAh/g.The specific capacity of 5C is about 160mAh/g, and the capacity retention ratio after circulation 200 times is 81%, about 130mAh/g.
Comparative example 1
[manufacture of lithium-rich manganese-based anode material presoma]
In addition to using sodium carbonate as the NH in precipitating reagent alternative embodiment 14HCO3Except, with side same as Example 1
Formula prepares the presoma of lithium-rich manganese-based anode material.
[analysis of lithium-rich manganese-based anode material presoma]
Analysis same as Example 1 is carried out to the resulting lithium-rich manganese-based anode material presoma of comparative example 1.Its XRD diagram
Spectrum shows the NaC in Fig. 1, and SEM illustrates (a) in Fig. 2.Analysis the result shows that, gained presoma be metal carbonate, it is micro-
Seeing pattern is threadiness.The average grain diameter of gained threadiness presoma is about 15nm.
[manufacture of lithium-rich manganese-based anode material]
In addition to the lithium-rich manganese-based anode material of the manufacturing method preparation of the lithium-rich manganese-based anode material presoma using comparative example 1
Except material precursor, lithium-rich manganese-based anode material is prepared in the same manner as in Example 1.By resulting lithium-rich manganese-based anode material
After material carries out gas displacement in gas ventilator, sealed up for safekeeping with dry argon gas.
[analysis of lithium-rich manganese-based anode material]
Analysis same as Example 1 is carried out to the resulting lithium-rich manganese-based anode material of comparative example 1.Its XRD spectrum is shown
NaC in Fig. 3, SEM illustrate (a) in Fig. 4.Analysis the result shows that, by material synthesized by this technique do not have heap
Pile structure.Gained lithium-rich manganese-based anode material is the particle of the irregular shape of average diameter about 200nm.
[production of lithium ion battery]
The lithium ion battery of comparison example 1 by the way of same as Example 1, and using same as Example 1
Mode evaluates battery.The result shows that the specific capacity of 0.1C is about 192mAh/g, the specific capacity 104mAh/g of 1C, circulation
Capacity retention ratio after 100 times is 95%, about 99mAh/g.And the specific capacity of 5C is only about 40mAh/g.It is obvious that with implementation
Example 1 is compared with 2, and the chemical property of the positive electrode is poor, especially the property under the conditions of high current (such as 5C) charge and discharge
Energy difference becomes apparent.
Comparative example 2
[manufacture of lithium-rich manganese-based anode material presoma]
(1) under room temperature, with stoichiometric ratio 54:13:13, by MnSO4·H2O、NiSO4·6H2O and CoSO4·
7H2O is dissolved in deionized water, and being made into volume is 1L, and concentration is the mixed ion solutions A of 2mol/L.By Na2CO3It is dissolved in deionization
In water, it is made into the solution B of 2mol/L.Ammonium hydroxide is dissolved in deionized water, the solution C of 0.2mol/L is made into.
(2) using the microsyringe 1 and 2 with model, respectively with the rate of 5ml/min to mixed ion solutions A, simultaneously
Solution B and solution C is added dropwise, is kept stirring, the pH value of the suspension as obtained by the regulation of the additional amount of solution B and solution C itself, directly
To gained suspension pH to 8 when stop be added dropwise, continue stir 15h to react fully.
(3) after being aged 15h, gained precipitating is filtered, then the deionized water that 5L is added in filter cake is washed and (is filled
Divide stirring).So technique is filtered, washed alternately, until 1mol/LBaCl is added dropwise2After solution, filtrate is heavy without white
Until shallow lake or Tyndall phenomenon.The qualified precipitating of washing is finally placed in 100 DEG C of vacuum oven dry 12h.
[analysis of lithium-rich manganese-based anode material presoma]
Analysis same as Example 1 is carried out to the resulting lithium-rich manganese-based anode material presoma of comparative example 2.Its XRD diagram
Spectrum shows the NaHC in Fig. 1, and SEM illustrates (b) in Fig. 2.Analysis the result shows that, gained presoma be threadiness it is microcosmic
The average grain diameter of pattern, gained threadiness presoma is about 15nm.
[manufacture of lithium-rich manganese-based anode material]
In addition to the lithium-rich manganese-based anode material of the manufacturing method preparation of the lithium-rich manganese-based anode material presoma using comparative example 2
Except material precursor, lithium-rich manganese-based anode material is prepared in the same manner as in Example 1.By resulting lithium-rich manganese-based anode material
After material carries out gas displacement in gas ventilator, sealed up for safekeeping with dry argon gas.
[analysis of lithium-rich manganese-based anode material]
Analysis same as Example 1 is carried out to the resulting lithium-rich manganese-based anode material of comparative example 2.Its XRD spectrum is shown
NaHC in Fig. 3, SEM illustrate (b) in Fig. 4.Analysis the result shows that, by material synthesized by this technique be without
Stacking provisions.Gained lithium-rich manganese-based anode material is the particle of the irregular shape of average diameter about 200nm.
[production of lithium ion battery]
The lithium ion battery of comparison example 2 by the way of same as Example 1, and using same as Example 1
Mode evaluates battery.The result shows that the specific capacity of 0.1C is about 220mAh/g, the specific capacity of 1C is about 175mAh/g,
Capacity retention ratio after circulation 100 times is 93%.The specific capacity of 5C is only about 75mAh/g.It is obvious that with Examples 1 and 2 phase
Than chemical property is poor, and especially the performance difference under the conditions of high current (such as 5C) charge and discharge becomes apparent.
Fig. 5 shows embodiment 1 (NHC) and comparative example 2 (NaHC), the XRD spectrum (office of obtained lithium-rich manganese-based anode material
Portion).From map as can be seen that NHC diffraction peaks broadening it is more serious, intensity is lower, show embodiment 1 it is lithium-rich manganese-based just
Pole material has apparent stacking provisions.The diffraction maximum of NaHC has apparent peak structure, show comparative example 2 it is lithium-rich manganese-based just
Pole material does not have stacking provisions.
Fig. 6 is shown under the current density of 0.1C, the specific volume of lithium-rich manganese-based anode material prepared by embodiment 1 (NHC)
It measures and is compared with the specific capacity of lithium-rich manganese-based anode material prepared by comparative example 2 (NaHC).It is obvious that the electric discharge of embodiment 1
Specific capacity is apparently higher than comparative example 2, and cyclical stability is also better than comparative example 2.
Fig. 7 indicates the specific capacity of lithium-rich manganese-based anode material prepared by embodiment 1 (NHC) under the current density of 5C
Compare with the specific capacity of lithium-rich manganese-based anode material prepared by comparative example 2 (NaHC).It is obvious that the electric discharge specific volume of embodiment 1
Amount is higher than comparative example 2, and cyclical stability is also superior to comparative example 2.
Fig. 8 shows richnesses prepared by lithium-rich manganese-based anode material prepared by embodiment 1 (NHC) and comparative example 2 (NaHC)
The high rate performance of lithium manganese-based anode material compares.Obviously, the lithium-rich manganese-based anode with stacking provisions prepared using embodiment 1
Material, the performance under different current densities are all higher than comparative example 2.And lithium-rich manganese-based anode prepared by embodiment 1
The high-rate performance of material is also apparently higher than comparative example 2.
Claims (10)
1. a kind of preparation method of the presoma of the lithium-rich manganese-based anode material with stacking provisions, the method includes following steps
It is rapid:
(1) according to set stoichiometric ratio, manganese salt and cobalt salt and optional nickel salt is soluble in water, it is configured to mixed metal
The solution A of salt；Weak acid and mild base salt is soluble in water, it is configured to solution B, the preferred NH of the weak acid and mild base salt4HCO3And/or
(NH4)2CO3；
(2) in the case where the lasting stirring solution A, the solution B is at the uniform velocity added in the solution A, or is continued
In the case where stirring the solution B, the solution A is at the uniform velocity added in the solution B, during addition, is only passed through
The additional amount of the solution B or the solution A come regulate and control gained suspension pH value, until the pH value of gained suspension is in 7-
Between 8.5, preferably between 7-8, stop that the solution B or the solution A is added, continuing stirring to reaction terminates；
(3) by step (2) resulting reaction product after post treatment process can be obtained with stacking provisions it is lithium-rich manganese-based just
The carbonate precursor of pole material.
2. the preparation method of the presoma of the lithium-rich manganese-based anode material according to claim 1 with stacking provisions,
Described in solution A mixed metal salt concentration be 0.02-5mol/L, preferably 0.1-3mol/L, more preferable 0.5-2.5mol/L,
And/or the concentration of the solution B is 0.02-5mol/L, preferably 0.5-2.5mol/L.
3. the preparation method of the presoma of the lithium-rich manganese-based anode material according to claim 1 with stacking provisions,
The speed in the solution B is added by speed that the solution B is added in the solution A or by the solution A in middle step (2)
Degree is 0.05-50mL/min, preferably 1-20mL/min.
4. the preparation method of the presoma of the lithium-rich manganese-based anode material according to claim 1 with stacking provisions,
Described in postprocessing working procedures in step (3) include ageing, separation, washing and drying steps, it is preferable that digestion time 5-
48h, more preferably 10-24h.
5. the preparation method of the presoma of the lithium-rich manganese-based anode material according to claim 1 with stacking provisions,
Described in manganese salt described in step (1) be selected from one or more of manganese sulfate, manganese nitrate or manganese acetate, it is described
Nickel salt is selected from one or more of nickel sulfate, nickel nitrate and nickel acetate, and the cobalt salt is selected from cobaltous sulfate, cobalt nitrate
Or one or more of cobalt acetate.
6. the preparation method of the presoma of the lithium-rich manganese-based anode material according to claim 1 with stacking provisions,
Described in the lithium-rich manganese-based anode material with stacking provisions presoma be the carbonate with nanocluster microscopic appearance before
Drive body.
7. a kind of preparation method of the lithium-rich manganese-based anode material with stacking provisions, which comprises
Pass through the system of the presoma of the lithium-rich manganese-based anode material according to claim 1-6 with stacking provisions
Preparation Method preparation has the presoma of the lithium-rich manganese-based anode material of stacking provisions；
The presoma of lithium-rich manganese-based anode material obtained with stacking provisions and lithium salts are mixed, by gained mixture logical
Have and carries out pre-burning and secondary clacining in the heat treatment equipment of air or oxygen to get the lithium-rich manganese-based anode with stacking provisions
Material.
8. the preparation method of the lithium-rich manganese-based anode material according to claim 7 with stacking provisions, wherein the lithium
Salt is lithium carbonate and/or lithium hydroxide and/or the lithium salts excess 2-10wt.%, preferably 3-10wt.%.
9. the preparation method of the lithium-rich manganese-based anode material according to claim 7 or 8 with stacking provisions, wherein described
The temperature of pre-burning controls between 350-600 DEG C and/or the soaking time of the pre-burning is 2-8h and/or the secondary clacining
Temperature be 700-1000 DEG C and/or the soaking time of the secondary clacining is 5-20h.
10. the preparation method of the lithium-rich manganese-based anode material according to any one of claims 7 to 9 with stacking provisions,
Its further comprise by the lithium-rich manganese-based anode material obtained with stacking provisions in atmosphere exchange system set in addition
Gas displacement is carried out to be sealed up for safekeeping in drying argon gas/nitrogen preferably without carbon dioxide, in inert gas preferably in the gas
Contain gas absorption and dried reagent in atmosphere exchange system, the preferably described gas absorption and dried reagent are 3A/4A molecular sieve, hydrogen
Sodium oxide molybdena and sodium carbonate.
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