CN104701489B - A kind of lithium ion battery anode active material, its preparation method and application - Google Patents
A kind of lithium ion battery anode active material, its preparation method and application Download PDFInfo
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Abstract
This application discloses a kind of lithium ion battery anode active material, it is characterised in that including core-shell material；At least one of the core of the core-shell material in silicon, the oxide of silicon, tin, the oxide of tin；The shell of the core-shell material is coated on core surface by organic compound and formed, at least one of the organic compound in the compound containing phosphatide base, carbonyl, hydroxyl and amino.Silica-base material/tin-based material is coated by using organic compound, silica-base material/tin-based material is effectively inhibited to be used as the bulk effect of lithium ion battery anode active material, the polarization of battery is reduced, so as to greatly improve the energy density and cycle performance of lithium ion battery.
Description
Technical field
The application is related to a kind of lithium ion battery negative material, belongs to field of lithium ion battery.
Background technology
Lithium ion battery because with higher energy density, have extended cycle life, operating voltage is high, memory-less effect and environment
Friendly the advantages of, it is widely used in fields such as portable type electronic product, accumulation power supplies.
As lithium ion battery anode active material, silica-base material is relative to the graphite material being widely used at present, because of tool
There are higher theoretical specific capacity (4200mAh/g), the de- lithium current potential (being less than 0.5V) and greater security energy of relatively height, by
Extensive concern.However, the electrical conductivity of silicon itself is relatively low, in electrochemistry cyclic process, Lithium-ion embeding/abjection can cause silicon substrate
More than 300% expansion/contraction occurs for the volume of material, the structure collapses of silica-base material is caused, so as to cause the energy of battery
Density and cycle performance are greatly reduced.
To improve silicon based anode material structural instability caused by Volume Changes, current common method is by carbon material
Be coated on silicon grain surface, to improve the cycle performance of battery, but the technique exist operating time length, mix it is uneven, after
The shortcomings for the treatment of temperature height and high energy consumption.In addition, the method that also useful polymer is coated to silicon/tin particles surface, the party
Although method can improve the electron conduction of material, it cannot be guaranteed that lead lithium ion, therefore exist in cyclic process larger
Polarization problem, and the poor toughness of such material, it is impossible to bear the Volume Changes of material, cause clad to come off.
The content of the invention
According to the one side of the application there is provided a kind of lithium ion battery anode active material, by using organic compound
Thing is coated to silica-base material/tin-based material, effectively inhibits silica-base material/tin-based material is in lithium ion abjection/to be embedded in
Bulk effect in journey, for lithium ion battery, can reduce the polarization of battery, so as to greatly improve the energy of lithium ion battery
Density and cycle performance.
The lithium ion battery anode active material, it is characterised in that include core-shell material；
At least one of the core of the core-shell material in silicon, the oxide of silicon, tin, the oxide of tin；
The shell of the core-shell material is coated on core surface by organic compound and formed, and the organic compound, which is selected from, contains phosphorus
At least one in ester group, carbonyl, the compound of hydroxyl and amino.
As one kind preferred embodiment, the core of the core-shell material is the oxide S iO of siliconx(wherein, 0.5<x≤
3.0)。
Preferably, the silicon is to be handled by the concentrated sulfuric acid and mixed solution of hydrogen peroxide, and surface carries the silicon of hydroxyl；It is described
Tin is to be handled by the concentrated sulfuric acid and mixed solution of hydrogen peroxide, and surface carries the tin of hydroxyl.
The phosphide base has construction unit shown in formula I：
Wherein, at least one in No. 1 oxygen atom and No. 2 oxygen atoms is connected with carbon atom.
The amino is selected from-NH2,-NHR or-NR2；R is selected from the alkyl that carbon number is 1~20.
Silicon, the oxide of silicon, tin, the oxide material of tin are as the core of core-shell material, and surface has hydroxyl, can with containing
The compound for having phosphide base, carbonyl, hydroxyl and amino is connected by hydrogen bond action, so as to form stable cladding on its surface
Layer.Compound containing phosphide base, carbonyl, hydroxyl and amino has certain elasticity, can effectively press down in charge and discharge process
The Volume Changes of core processed.In addition, an oxygen on shell phosphide base is negatively charged (formula 1), can in charge and discharge process, be lithium from
Son provides transmission channel, and containing free on nitrogen on the double bond oxygen on phosphide base, the oxygen on carbonyl, hydroxyl oxygen and amino
Electron orbit, transmission channel can be provided for electronics, so as to improve the electric conductivity of lithium ion, the polarization of battery is advantageously reduced
Effect, so as to improve cyclical stability and the life-span of battery.
Preferably, the compound containing phosphide base, carbonyl, hydroxyl and amino is selected from nucleotides, the combination of nucleotides
At least one in thing, nucleotide derivative, the composition of nucleotide derivative.
The nucleotide derivative is included in addition to ribonucleotide and deoxyribonucleotide, and other are by phosphoric acid, sugar
Quasi-molecule and the compound of alkaloid formation.
Preferably, the nucleotide derivative is selected from adenosine diphosphate (ADP), atriphos, GTP, 3 ', 5 '-ring
At least one in shape adenylate.
Contain the compound of phosphide base, carbonyl, hydroxyl and amino relative to other, the shell of compound formation preferably, more
It can improve the lithium ion conducting performance of negative active core-shell material, and because the group interacted with core surface hydroxyl is more, more
The stability of shell clad can be significantly improved, the effect for suppressing the Volume Changes of core-shell material center is also more obvious.
Preferably, at least one of the composition of nucleotides in base-pair, single stranded DNA, double-stranded DNA, RNA.Arbitrarily
The single stranded DNA of length, double-stranded DNA, RNA are used equally for the technical scheme of the application.
Preferably, percentage composition of the shell of the core-shell material in core-shell material is 0.02~10wt%.When nucleocapsid material
Weight/mass percentage composition of the shell of material in core-shell material within this range, is more beneficial for while ensureing the ion of negative active core-shell material
The electric conductivity of conductive performance and electronics.It is further preferred that percentage composition of the shell of the core-shell material in core-shell material is
0.1~5wt%.
Preferably, the median of the core of the core-shell material is 50nm~10 μm.It is further preferred that the nucleocapsid material
The median of the core of material is 100nm~1 μm.
Preferably, in the lithium ion battery anode active material, the weight/mass percentage composition of core-shell material is no less than 90%.
It is further preferred that in the lithium ion battery anode active material, the lower limit of the weight/mass percentage composition of core-shell material be selected from but
It is not limited to 92%, 95%, 98%, 99%.It is further preferred that the lithium ion battery anode active material is nucleocapsid material
Material, i.e., weight/mass percentage composition of the described core-shell material in lithium ion battery anode active material is 100%.
According to the another aspect of the application there is provided the method for core-shell material in above-mentioned lithium ion battery anode active material,
Characterized in that, at least comprising the following steps：
(a) organic compound is dissolved in water, is placed at a temperature of 10~100 DEG C, obtains containing the molten of organic compound
Liquid；
(b) at least one in silicon, the oxide of silicon, tin, the oxide of tin is placed in step (a) resulting solution, mixed
Close uniform, the core-shell material is produced after drying.
Preferably, organic compound is is dissolved in water by step (a), is placed at 10~100 DEG C ultrasonic, obtains containing having
The solution of machine compound.It is further preferred that the ultrasonic time is 0~1 minute.It is further preferred that the ultrasonic time
For 2 seconds~1 minute.
Preferably, temperature described in step (a) is 30~80 DEG C.
Preferably, step (a) is placed in ultrasound 0~1 minute at 10~100 DEG C, obtained for organic compound is dissolved in water
To the solution containing organic compound.It is further preferred that step (a) for organic compound is dissolved in water, be placed in 30~
Ultrasound 2 seconds~1 minute, obtains the solution containing organic compound at 80 DEG C.
According to the another aspect of the application there is provided a kind of lithium-ion negative pole piece, including collector and it is coated in negative pole currect collecting
Cathode membrane on body, it is characterised in that contain any of the above-described lithium ion battery anode active material, root in the cathode membrane
At least one in the lithium ion battery anode active material prepared according to any of the above-described method.
The cathode membrane is coated in collection by the slurry containing lithium ion battery anode active material, conductive agent and binding agent
Obtained on fluid.
The weight/mass percentage composition in cathode membrane of described conductive agent is 5%~10%.
At least one of the conductive agent in activated carbon, CNT, graphene.
The preparation method of the lithium-ion negative pole piece, it is characterised in that at least comprise the following steps：
(a) organic compound is dissolved in water, is placed in ultrasound at 10~100 DEG C, obtains containing the molten of organic compound
Liquid；
(b) at least one in silicon, the oxide of silicon, tin, the oxide of tin is placed in step (a) resulting solution, mixed
After closing uniformly, through being dried to obtain core-shell material；
(c) it is core-shell material obtained by step (b) is uniform with conductive agent, binding agent and dispersant, obtain cathode size；
(d) cathode size is coated in the surface of negative current collector, the negative plate is produced through drying, roll-in.
According to the another aspect of the application, there is provided a kind of lithium ion battery, it is characterised in that contains any of the above-described lithium ion
At least one in GND active material, the lithium ion battery anode active material prepared according to any of the above-described method
Kind.
The lithium ion battery includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, negative current collector
And it is coated on cathode membrane, barrier film and electrolyte on negative current collector.
The positive pole diaphragm includes positive electrode active materials, binding agent and conductive agent.
The cathode membrane includes negative active core-shell material, binding agent and conductive agent.
The positive electrode active materials are optionally from cobalt acid lithium (LiCoO2), nickel cobalt aluminium ternary material (being abbreviated as NCA), nickel cobalt manganese
Ternary material (being abbreviated as NCM), LiMn2O4 (LiMnO2), LiFePO4 (LiFePO4) at least one.
The negative active core-shell material is selected from any of the above-described lithium ion battery anode active material, according to any of the above-described method system
At least one in standby obtained lithium ion battery anode active material.
The beneficial effect that the application can be produced at least includes：
(1) lithium ion battery anode active material provided herein, by using containing phosphide base, carbonyl, hydroxyl
Silica-base material/tin-based material is coated with the compound of amino, silica-base material/tin-based material is effectively inhibited in lithium ion
Bulk effect in abjection/telescopiny, and clad has very high stability.
(2) preparation method of lithium ion battery anode active material provided herein, technique is simple, low cost, favorably
In industrial applications.
(3) lithium ion battery provided herein, with higher energy density and cyclical stability.
Embodiment
The present invention is described in detail below by embodiment, but the invention is not limited in these embodiments.
In embodiment, binding agent polyvinylidene fluoride (being abbreviated as PVDF) is purchased from Shenzhen Tai Neng new materials Co., Ltd；Carboxylic
Sodium carboxymethylcellulose pyce thickener (being abbreviated as CMC) is purchased from Zhengzhou Zhi Yi chemical products Co., Ltd；Conductive black Super-P is purchased from
Te Migao companies of Switzerland；Bonding agent butadiene-styrene rubber (being abbreviated as SBR) is purchased from LG chemistry.
In embodiment, double-stranded DNA, single stranded DNA, RNA, base-pair and deoxynucleotide are purchased from the biological sections of Shanghai Suo Laibao
Skill Co., Ltd.
In embodiment, used silica flour, silicon dioxide powder SiO2、SiO1.5Powder, glass putty, SnO2The median of powder exists
Between 50nm~10 μm.Wherein, silica flour and glass putty pass through Piranha solution (piranha solution, the volume ratio concentrated sulfuric acid：H2O2=3：
1) 0.5h is handled at 85 DEG C.The chemical property of battery is determined using the Autolab types electrochemical workstation of Wan Tong companies of Switzerland.
The preparation of embodiment negative plate
The preparation process of core-shell material is：After organic compound is dissolved in ultra-pure water, at a certain temperature ultrasound one
Section time (supersonic frequency is 20KHZ), obtains the solution containing organic compound, the percentage composition of organic compound is Awt%；
Silica-base material/tin-based material of B parts by weight is added in the solution that C parts by weight contain organic compound, mixing and stirring
Afterwards, water removal is gone in 80 DEG C of dryings, obtains core-shell material.
The preparation process of negative plate is：Core-shell material (is write a Chinese character in simplified form with conductive agent activated carbon and binding agent polyvinylidene fluoride
For PVDF, 10%) weight/mass percentage composition of polyvinylidene fluoride is, (is abbreviated as in solvent N-methyl pyrilidone in binding agent
NMP it is uniformly dispersed in), forms cathode size.Solids content is 50wt% in cathode size, comprising Xwt% in solid constituent
Core-shell material, Ywt% conductive agent activated carbon, Zwt% PVDF.Cathode size is uniformly coated to thickness negative for 12 μm
On the copper foil of affluxion body of pole, coating weight is 0.0089g/cm2, then at 85 DEG C dry after be cold-pressed, trimming, cut-parts, slitting,
6h is dried under 85 DEG C of vacuum conditions afterwards, soldering polar ear produces negative plate.
Core-shell material numbering, the numbering of negative plate and raw material type, consumption, the weight percentage and preparation condition of shell
Relation it is as shown in table 1.
Table 1
*：It is heated only to 60 DEG C, it is not ultrasonic.
The negative plate DN1 of comparative example 1 preparation
Core-shell material DH1 preparation：
Specific steps and condition are with core-shell material H5 preparation, and difference is, in the solution containing single stranded DNA, single
The percentage composition (Awt%) of chain DNA is 2wt%.In gained core-shell material DH1, the weight percent of the shell of single stranded DNA formation contains
Measure as 20wt%.
Negative plate DN1 preparation：
Specific steps and condition are with negative plate N5 preparation, and difference is, by the core-shell material H5 in cathode size
Change DH1 into, gained negative plate is designated as DN1.
The negative plate DN2 of comparative example 2 preparation
Silicon and conductive agent activated carbon and binding agent polyvinylidene fluoride (are abbreviated as in PVDF, binding agent gathering inclined difluoro second
The weight/mass percentage composition of alkene forms negative pole slurry 10%), to be uniformly dispersed in solvent N-methyl pyrilidone (being abbreviated as NMP)
Material.Solids content is 50wt% in cathode size, the silicon comprising 90wt% in solid constituent, 3wt% conductive agent activated carbon,
7wt% PVDF.Cathode size is uniformly coated on the negative current collector Copper Foil that thickness is 12 μm, coating weight is
0.0089g/cm2, be cold-pressed after then being dried at 85 DEG C, trimming, cut-parts, slitting, it is dry under 110 DEG C of vacuum conditions afterwards
Dry 4h, soldering polar ear produces negative plate DN2.
The negative plate DN3 of comparative example 3 preparation
By tin oxide SnO2(it is abbreviated as gathering in PVDF, binding agent with conductive agent activated carbon and binding agent polyvinylidene fluoride
10%) weight/mass percentage composition of vinylidene fluoride is, is uniformly dispersed in solvent N-methyl pyrilidone (being abbreviated as NMP), shape
Into cathode size.Solids content is 50wt% in cathode size, and 90wt% SnO is included in solid constituent2, 3wt% conduction
The PVDF of agent activated carbon, 7wt%.Cathode size is uniformly coated on the negative current collector Copper Foil that thickness is 12 μm, coating
Measure as 0.0089g/cm2, then at 85 DEG C dry after be cold-pressed, trimming, cut-parts, slitting, afterwards in 110 DEG C of vacuum conditions
Lower dry 6h, soldering polar ear produces negative plate DN3.
Using the making of the lithium ion battery of negative plate obtained by embodiment and comparative example
The preparation of positive plate：
By positive electrode active materials cobalt acid lithium (molecular formula LiCoO2), conductive agent conductive black Super-P, binding agent gather inclined two
(weight/mass percentage composition for being abbreviated as polyvinylidene fluoride in PVDF, binding agent is 10%) in Solvents N-methyl pyrrolidines to PVF
It is uniformly dispersed in ketone (being abbreviated as NMP), anode sizing agent is made.Solids content is bag in 75wt%, solid constituent in anode sizing agent
The PVDF and 1.4wt% of cobalt acid lithium, 1.6wt% containing 97wt% conductive black Super-P.Anode sizing agent is equably coated with
In thickness on 16 μm of plus plate current-collecting body aluminium foil, coating weight is 0.018g/cm2.Be cold-pressed after then being dried at 85 DEG C,
Trimming, cut-parts, slitting, dry 4h under 85 DEG C of vacuum conditions afterwards, and soldering polar ear produces positive plate.
The preparation of electrolyte
In drying shed, by ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate (letter
It is written as DEC) EC in mass ratio:PC:DEC=30:30:40 ratio is well mixed, and obtains non-aqueous organic solvent.To non-aqueous organic
LiPF is added in solvent6, obtain LiPF6Concentration is 1mol/L solution, as electrolyte.
The preparation of lithium ion battery：
Polyethylene film using 12 μm is used as barrier film.
Negative plate N1~N27, the negative plate DN1~DN3 of the preparation of comparative example 1~3 prepared respectively with embodiment 1, as
Negative plate, the preparation as lithium ion battery.Before prepared by lithium ion battery, the thickness of each negative plate is recorded respectively.
Concretely comprise the following steps：
Positive plate, barrier film, negative plate are folded in order, barrier film is in the work for playing isolation in the middle of both positive and negative polarity
With it is that 8mm, width are the square naked battery core that 60mm, length are 130mm to be then wound into thickness.Naked battery core is loaded into Aluminium Foil Package
Pack, the vacuum bakeout 10h at 75 DEG C injects nonaqueous electrolytic solution, by Vacuum Package, standing 24h, 0.1C is used afterwards
Then the constant current charge of (160mA) drops to 0.05C (80mA) to 4.2V with 4.2V constant-voltage charges to electric current, then with
0.1C (160mA) constant current is discharged to 3.0V, is repeated 2 times discharge and recharge, finally with 0.1C (160mA) constant current charge
To 3.8V, that is, complete the preparation of lithium rechargeable battery.
The lithium ion battery prepared respectively by negative plate of N1~N27, is designated as lithium ion battery C1~C27 respectively；Respectively
The lithium ion battery prepared by negative plate of DN1~DN3, is designated as lithium ion battery DC1~DC3 respectively.
Embodiment and the cycle performance of lithium ion battery obtained by comparative example are tested
Lithium rechargeable battery C1~C27 and DC1~DC3 cycle performance is tested respectively.
Specific method is：4.3V is first charged to lithium rechargeable battery with 1C constant current at 25 DEG C, then with
4.3V constant-potential charges to electric current is 0.05C, is then discharged to 3.0V to lithium rechargeable battery with 1C constant current, this
The discharge capacity circulated for a charge and discharge cycles process, this discharge capacity for first time.Stand after half an hour, by lithium
Ion secondary battery is circulated charge-discharge test in a manner described, respectively record the 100th time, 200 times, 300 times, 400 times and
The discharge capacity of 500 circulations, and calculate capability retention.
Capability retention (%)=[discharge capacity/the first of n-th circulation after the circulation of lithium rechargeable battery n-th
The discharge capacity of secondary circulation] × 100%.
Each lithium ion battery for passing through 500 circulations is disassembled, the thickness of anode strip, calculated thickness increase are measured respectively
Rate.
The thickness increment rate (%) of anode strip=(thickness-original depth after the 500th circulation)/original depth ×
100%.
Test result is as shown in table 2.
Table 2
According to the data in table 2, contrast C5, C9~C11, C20 and C21 result can be seen that in DNA content and ultrasound
In the case of the treatment time identical of vibration, with the increase of temperature, the capability retention of lithium ion battery also increases, and
The thickness increment rate that circulation is 500 times is gradually reduced also with the rise of temperature.But temperature it is too high when, such as C7, because DNA is in height
A small amount of decomposition is had under temperature, its content in cathode size is influenceed, causes the effect to the capability retention of battery smaller
And it is smaller to the volumetric expansion action effect of battery.
Contrast C1, C8, C11 can be seen that when the treatment temperature of sonic oscillation is identical, the increase of DNA content, then lithium from
The capability retention of sub- battery can also be improved.If by C22 as can be seen that DNA content is too high, the biography of lithium ion can be suppressed
Speed is passed, so as to increase the activation polarization of battery, causing the capacity of battery reduces, while suppressing the work of the volumetric expansion of battery
It can also be weakened with effect.
Contrast C4, C10, C18, C19 can be seen that the treatment time and DNA content identical in identical sonic oscillation
In the case of, double-stranded DNA is more relatively low compared to the capability retention of single stranded DNA, suppresses the action effect phase of the volumetric expansion of battery
To also weaker, it is more likely that be because cell negative electrode material in single stranded DNA avtive spot will be more than double-strand DNA so that
The binding sites number with negative active core-shell material is improved, increases the passage of lithium ion, so that it is steady to improve lithium ion battery circulation
It is qualitative, extend the service life of lithium ion battery.
Silicon, the oxide of silicon, tin, the oxide of tin are used equally for the skill of the application it can be seen from C1~C27 data
Art scheme, as core, the core-shell material for preparing the negative active core-shell material as lithium ion battery.
Contrasting C1~C17, DC2, DC3 data and can be seen that is had using the lithium ion battery of technical scheme
Good capability retention simultaneously can effectively suppress the volumetric expansion of battery.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent, improvement etc., should be included within the protection domain of the application.
Claims (9)
1. a kind of lithium ion battery anode active material, it is characterised in that including core-shell material；
At least one of the core of the core-shell material in silicon, the oxide of silicon, tin, the oxide of tin；
The shell of the core-shell material is coated on core surface by organic compound and formed, and the organic compound is selected from nucleotides, contained
There is at least one in the material, nucleotide derivative, the material containing nucleotide derivative construction unit of nucleotide building blocks
Kind.
2. lithium ion battery anode active material according to claim 1, it is characterised in that contain nucleotide building blocks
At least one of the material in base-pair, single stranded DNA, double-stranded DNA, RNA.
3. lithium ion battery anode active material according to claim 1, it is characterised in that the shell of the core-shell material exists
Percentage composition is 0.02~10wt% in core-shell material.
4. lithium ion battery anode active material according to claim 1, it is characterised in that the core of the core-shell material
Median is 50nm~10 μm.
5. prepare the method for core-shell material in any one of the Claims 1-4 lithium ion battery anode active material, its feature
It is at least to comprise the following steps：
(a) organic compound any one of claim 1 to 2 is dissolved in water, is placed at a temperature of 10~100 DEG C, obtains
To the solution containing organic compound；
(b) at least one in silicon, the oxide of silicon, tin, the oxide of tin is placed in step (a) resulting solution, mixing is equal
It is even, produce the core-shell material after drying.
6. method according to claim 5, it is characterised in that step (a) is placed in for organic compound is dissolved in water
It is ultrasonic at a temperature of 10~100 DEG C, obtain the solution containing organic compound.
7. method according to claim 5, it is characterised in that step (a) temperature is 30~80 DEG C.
8. a kind of lithium-ion negative pole piece, including collector and coating cathode membrane on a current collector, it is characterised in that described negative
Contain at least one in any one of Claims 1-4 lithium ion battery anode active material in the diaphragm of pole.
9. a kind of lithium ion battery, it is characterised in that contain any one of Claims 1-4 lithium ion battery negative activity
At least one in material.
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| CN113161551A (en) * | 2021-04-25 | 2021-07-23 | 宁德新能源科技有限公司 | Silicon-based negative electrode material, electrochemical device, and electronic device |
| CN117477059A (en) * | 2023-11-14 | 2024-01-30 | 浙江大学温州研究院 | Electrolyte for water-based zinc battery, application of electrolyte and water-based zinc battery |
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| CN102403506A (en) * | 2010-09-10 | 2012-04-04 | 威力能源股份有限公司 | Lithium ion battery negative electrode material additive, lithium ion battery and negative electrode material thereof |
| KR101579641B1 (en) * | 2012-05-30 | 2015-12-22 | 주식회사 엘지화학 | Negative active material for lithium battery and battery comprising the same |
| KR20140012464A (en) * | 2012-07-20 | 2014-02-03 | 삼성에스디아이 주식회사 | Silicon alloy based negative active material and composition including the same and method of manufacturing the same and lithium rechargeble battery |
| CN103682354B (en) * | 2012-09-18 | 2016-08-10 | 华为技术有限公司 | A kind of all-solid lithium-ion battery compound electrode material and preparation method thereof and all-solid lithium-ion battery |
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