CN104752709B - A kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor - Google Patents

A kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor Download PDF

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CN104752709B
CN104752709B CN201310743742.9A CN201310743742A CN104752709B CN 104752709 B CN104752709 B CN 104752709B CN 201310743742 A CN201310743742 A CN 201310743742A CN 104752709 B CN104752709 B CN 104752709B
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lithium
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manganese
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based anode
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CN104752709A (en
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庞国耀
庄卫东
卢世刚
尹艳萍
卢华权
高哲峰
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China Youyan Technology Group Co ltd
Youyan Technology Group Co ltd
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Beijing General Research Institute for Non Ferrous Metals
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses a kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor, comprise the following steps：(1) press molecular formula Mn of hydroxide precursorxCoyNi1‑x‑y(OH)2The molar ratio nickel salt of middle Mn, Co, Ni, cobalt salt, the mixed solution of manganese salt, wherein, 0.5 ＜ x ＜ 1,0 ＜ y ＜ 0.5, x+y ＜ 1；(2) prepare the alkaline aqueous solution containing additive；Prepare and contain EDTA, shitosan, the compound complex agent solution of ammonia；(3) under inert gas shielding; carry out successive reaction by nickel salt, cobalt salt, the mixed solution of manganese salt, alkaline aqueous solution, compound complex agent solution cocurrent injection successive reaction kettle; control EDTA, shitosan, the mean concentration of ammonium ion in reaction solution; pH value in reaction is controlled to be 9～13; reaction temperature is 30～80 DEG C, and mixing speed is 100～2000rpm；(4) reactor is naturally drained feed liquid to filter, wash, be dried.Using the lithium-rich manganese-based anode material hydroxide precursor of present invention preparation, composition uniformly, size tunable, growth fine and close.

Description

A kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor
Technical field
The present invention relates to a kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor, belong to lithium battery material Preparing technical field.
Background technology
The contradiction of energy demand and change that the increasingly depleted of the non-renewable energy resources such as oil, coal and the mankind grow with each passing day The considerable damage that the greenhouse gases of stone fuel combustion generation, pollutant etc. cause to environment, leads to current global warming, disease wantonly Cruel and natural disaster takes place frequently, and order is it was recognized that find the urgency of the alternative energy source of cleaning.With electric automobile and electrical network accumulation of energy For the lithium-ion-power cell of future generation of great application background, both can improve energy use efficiency, reduce greenhouse gases and dirt Those can be had the produced electric energy of the clean energy resourcies such as periodic wind energy, solar energy, tide energy again and carry out effectively by dye thing discharge Adjust, with energy saving.Under the primary condition meeting the aspects such as safe and environment-friendly, cost, life-span, Key Performance Indicator is high Energy density and repid discharge ability. for example, beautiful, Deng state requires to reach to the energy density of lithium-ion-power cell of future generation 300Wh/kg, is more than 2 times of the lithium iron phosphate dynamic battery energy density currently developing.The low capacity of positive electrode Become the bottleneck improving lithium ion battery energy density further, need the novel anode material of exploitation higher capacity badly.In recent years Carry out stratiform richness lithium Mn base anode material xLi2MnO3·(1-x)LiMO2(M is Mn, Ni, Co or a combination thereof) has Fabrication of High Specific Capacitance because of it The unusual electrifications such as amount (200～300mAh/g), inexpensive, outstanding circulation ability and new charge discharge mechanism Learn performance to be received significant attention, be seen as positive electrode current commercialization main product LiCoO2Succedaneum well.This material Mainly based on manganese element, and manganese is cheap, and energy density is higher, more friendly to environment, is lithium ion One of direction of positive electrode development.
The spherical anode material synthetic technology of industrialization usually first prepares spherical precursor, then heat after mixing with lithium source Process obtains material requested.But there is many asking in order to prepare the precursor technique of rich lithium manganese base solid solution positive electrode at present Topic：If it does precipitant using alkaline hydrated oxide first, due to Mn (OH)2Solubility product Ksp=1.9 × 10-13Hence it is evident that it is high In Ni (OH)2With Co (OH)2(respectively 2.0 × 10-15With 1.6 × 10-15), it is easily caused that presoma primary particle is tiny, transition Metallic element composite distribution lack of homogeneity, also can easily the moisture absorption oxidized, and primary particle particle diameter is tiny is unfavorable for surface modification, Hardly result in the modified product of stable and consistent.So in order to obtain spherical morphology during precursor synthesis, general employing is added Chelating agent suppresses into nuclear reaction.But prior art typically adopts ammonia etc. as single chelating agent, high Mn content precursor crystal Based on one-dimensional or two-dimensional growth, between primary particle, arch formation substantially, causes material tap density low for growth；And according to Carbonate be precipitant although balling-up is good, but be not easily controlled particle size distribution, and final richness Mn-based material electrical property produced Raw material impact；Secondly tap density is low, and surface residual alkali amount may be very high, and it is unfavorable that cycle life and specific energy raising are had Impact.These unfavorable factors suppress its business-like development.
Patent documentation CN102881886A discloses a kind of before being precipitant low temperature preparation richness lithium solid solution using carbonate The method of body, the method embodiment is obtained only 1～3 μm of lithium solid solution cathode material particle diameter of richness, and particle diameter is less to lead to material to add Work poor-performing.
Content of the invention
It is an object of the invention to provide a kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor.
For achieving the above object, the present invention employs the following technical solutions：
A kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor, comprises the following steps：
(1) according to molecular formula Mn of hydroxide precursorxCoyNi1-x-y(OH)2The molar ratio nickel of middle Mn, Co, Ni Salt, cobalt salt, the mixed solution of manganese salt, wherein, 0.5 ＜ x ＜ 1,0 ＜ y ＜ 0.5, x+y ＜ 1；
(2) prepare the alkaline aqueous solution containing additive；Prepare the compound complex agent containing EDTA, shitosan, ammonia molten Liquid；
(3) under inert gas shielding, will be water-soluble to nickel salt, cobalt salt, the mixed solution of manganese salt, the alkalescence containing additive Carry out successive reaction in liquid and the injection successive reaction kettle of the compound complex agent solution cocurrent containing EDTA, shitosan, ammonia, Control reaction solution in EDTA, shitosan, the mean concentration of ammonium ion, and control reaction solution pH value be 9～13, reaction Temperature is 30～80 DEG C, and mixing speed is 100～2000rpm；
(4) reactor natural excrement feed liquid is filtered, washs, being dried to obtain lithium-rich manganese-based anode material hydroxide forerunner Body.
Wherein, described nickel salt, manganese salt, cobalt salt are respectively one or more of sulfate, nitrate or chlorate.Described In nickel salt, cobalt salt, the mixed solution of manganese salt, nickel ion, cobalt ion, the total mol concentration of manganese ion are 0.8～3.0mol/L, excellent Elect 0.8～2.8mol/L, more preferably 1.0～2.5mol/L as.
Wherein, described alkaline aqueous solution is the mixed solution of one or more of NaOH, KOH and LiOH aqueous solution.Alkali Property aqueous solution in OH molar concentration be 1～12mol/L, preferably 1.6～10mol/L, more preferably 3～8mol/L.
Wherein, described additive be polyvinyl pyridine, polyacrylamide, polyethyleneimine one or more, alkaline water In solution, the mass concentration of additive is 0.01%～0.3%, preferably 0.02%～0.3%.More preferably 0.05%～ 0.2%.
In described step (3), the pH of reaction solution is preferably 9～12, more preferably 9.5～11.5；Reaction temperature is preferably 40～80 DEG C, more preferably 40～70 DEG C；Mixing speed is preferably 100～1800rpm, more preferably 100～1000rpm.
Wherein, in described reaction solution, the molar average concentration of EDTA controls in 0.0001～0.3mol/L, preferably 0.001～0.2mol/L, more preferably 0.05～0.15mol/L；The average quality concentration of shitosan controls 0.01%～ 20%, preferably 0.03%～19%, more preferably 0.04%～18%；The molar average concentration of ammonium ion controls 0.01 ～4mol/L, preferably 0.2～3.5mol/L, more preferably 0.2～2mol/L.
Preparation-obtained lithium-rich manganese-based anode material hydroxide precursor is spherical in shape or spherical, and D50 is 5～20 μ M, and tap density is more than 1.3g/cm3.
It is an advantage of the current invention that：
The present invention adopts the rich lithium solid solution cathode material precursor of hydroxide coprecipitation step preparation, by controlling preparation temperature Spend, adopt compound complex agent system and add a series of technology such as additive.Achieve the tune to precursor crystal growth Control, so synthesize component uniformly, the fine and close spherical richness lithium solid solution cathode material precursor of size tunable, growth.
Lithium-rich manganese-based anode material hydroxide precursor using present invention preparation is used for preparing lithium-rich manganese-based anode material Material, obtained lithium-rich manganese-based anode material tap density is more than 1.3g/cm3, capacity is more than 240mAh/g.
Brief description
Fig. 1 is the particle size distribution figure of embodiment 3 sample.
Fig. 2 is the rich lithium manganese positive pole charging and discharging curve figure of embodiment 3 gained precursor preparation.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 4 sample.
Specific embodiment
The invention will be further described by the following examples, but the present invention is not limited to following examples.
Embodiment 1
By NiSO4、CoSO4、MnSO4In molar ratio Mn: Ni: Co=55: 25: 20 proportions nickel salts, cobalt salt, manganese salt mixed Heshui solution, nickel, cobalt, the hybrid ionic concentration of manganese are lmol/L, prepare the 8mol/L hydroxide containing 0.2% polyacrylamide Sodium solution, prepare the compound complex agent solution containing EDTA, shitosan and ammonia, then by nickel salt, cobalt salt, manganese salt mixing water Cocurrent pumps in reactor simultaneously for solution, aqueous slkali, compound complex agent solution, 70 DEG C of bath temperature, and speed of agitator is 1000rpm, the molar average concentration controlling EDTA in reaction solution is 0.15mol/L；The average matter of shitosan in reaction solution Amount concentration is 18%；In reaction solution, the molar average concentration of ammonium ion is 3mol/L, and control ph 11.5, is averagely stopped The time is stayed to be more than 15 hours, more than successive reaction 36h.The precipitate that overflow is obtained filters, washing, be dried after obtain rich lithium manganese Base anode material precursor.Gained lithium-rich manganese-based anode material precursor is in spherical, even particle size distribution, and D50 is 5 μm, holds Amount is more than 248mAh/g, tap density 1.45g/cm3.
Embodiment 2
By Ni (NO3)2、Co(NO3)2、Mn(NO3)2Mn: Ni: Co=65: 15: 20 proportions nickel salt, cobalt in molar ratio Salt, the mixed aqueous solution of manganese salt, nickel, cobalt, the hybrid ionic concentration of manganese are 2.5mol/L, prepare and contain 0.05% polyvinyl pyridine 3mol/L potassium hydroxide solution, prepare the compound complex agent solution containing EDTA, chitosan concentration and ammonia, then by nickel Cocurrent pumps in reactor simultaneously for salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution, bath temperature 70 DEG C, speed of agitator is 800rpm, and the molar average concentration controlling EDTA in reaction solution is 0.05mol/L；Shell in reaction solution The average quality concentration of polysaccharide is 0.04%；In reaction solution, the molar average concentration of ammonium ion is 0.2mol/L, and controls 9, mean residence time is more than 20 hours pH value, more than successive reaction 24h.The precipitate that overflow is obtained filters, washs, does Lithium-rich manganese-based anode material precursor is obtained after dry.Gained lithium-rich manganese-based anode material precursor is in spherical, and particle size distribution is equal Even, D50 is 6 μm, and capacity is more than 250mAh/g, tap density 1.6g/cm3.
Embodiment 3
By NiCl2、CoCl2、MnCl2Mn: Ni: Co=70: 20: 10 proportions nickel salt, cobalt salt, manganese salt in molar ratio Mixed aqueous solution, nickel, cobalt, the hybrid ionic concentration of manganese are 0.8mol/L, prepare the 1mol/L containing 0.01% polyethyleneimine Lithium hydroxide solution, prepares compound complex agent solution containing EDTA, shitosan and ammonia, then by nickel salt, cobalt salt, manganese salt Cocurrent pumps in reactor simultaneously for mixed aqueous solution, aqueous slkali, compound complex agent solution, 40 DEG C of bath temperature, and speed of agitator is 100rpm, the molar average concentration controlling EDTA in reaction solution is 0.0001mol/L；The average matter of shitosan in reaction solution Amount concentration is 0.01%；In reaction solution, the molar average concentration of ammonium ion is 0.1mol/L, and control ph is 9, averagely The time of staying is more than 24 hours, more than successive reaction 30h.The precipitate that overflow is obtained filters, washing, be dried after obtain rich lithium Manganese-based anode material precursor.Gained lithium-rich manganese-based anode material precursor is in spherical, even particle size distribution, as shown in figure 1, D50 is 9.3 μm, as shown in Fig. 2 adopting 0.1C rate charge-discharge, voltage range is 2.0-4.8V, and discharge capacity is more than 250mAh/g, tap density 1.45g/cm3.
Embodiment 4
By NiCl2、Co(NO3)2、MnSO4Mn: Ni: Co=70: 10: 20 proportions nickel salt, cobalt salt, manganese in molar ratio The mixed aqueous solution of salt, nickel, cobalt, the hybrid ionic concentration of manganese are 3mol/L, prepare and contain 0.2% polyethyleneimine and 0.1% The 6mol/ Lithium hydrate of polyacrylamide and 6mol/ sodium hydroxide solution, prepare compound containing EDTA, shitosan and ammonia Enveloping agent solution, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution, cocurrent pumps into simultaneously In reactor, 55 DEG C of bath temperature, speed of agitator is 1200rpm, and in control reaction solution, the molar average concentration of EDTA is 0.3mol/L；In reaction solution, the average quality concentration of shitosan is 20%；In reaction solution, the molar average of ammonium ion is dense Spend for 4mol/L, and control ph is 12, mean residence time is more than 20 hours, more than successive reaction 24h.Overflow is obtained Precipitate filter, washing, be dried after obtain lithium-rich manganese-based anode material precursor.As shown in figure 3, gained lithium-rich manganese-based anode material Material precursor is in spherical, even particle size distribution, and D50 is 10 μm, and capacity is more than 249mAh/g, tap density 1.8g/cm3.
Embodiment 5
By NiSO4、Co(NO3)2、MnCl2Mn: Ni: Co=70: 10: 20 proportions nickel salt, cobalt salt, manganese in molar ratio The mixed aqueous solution of salt, nickel, cobalt, the hybrid ionic concentration of manganese are 0.8mol/L, prepare containing 0.005% polyethyleneimine and The 0.8mol/L Lithium hydrate of 0.005% polyacrylamide and 0.8mol/L sodium hydroxide solution, prepare and contain EDTA, shitosan And the compound complex agent solution of ammonia, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution Cocurrent pumps in reactor simultaneously, 80 DEG C of bath temperature, and speed of agitator is 1800rpm, and in control reaction solution, EDTA's is average Molar concentration is 0.001mol/L；In reaction solution, the average quality concentration of shitosan is 0.03%；In reaction solution ammonium root from The molar average concentration of son is 0.2mol/L, and control ph is 9, and mean residence time is more than 15 hours, successive reaction 24h with On.The precipitate that overflow is obtained filters, washing, be dried after obtain lithium-rich manganese-based anode material precursor.Gained is lithium-rich manganese-based Anode material precursor is in spherical, even particle size distribution, and D50 is 10 μm, and capacity is more than 251mAh/g, tap density 1.62g/ cm3.
Embodiment 6
By Ni (NO3)2、CoSO4、MnCl2Mn: Ni: Co=60: 30: 10 proportions nickel salt, cobalt salt, manganese in molar ratio The mixed aqueous solution of salt, nickel, cobalt, the hybrid ionic concentration of manganese are 2.8mol/L, prepare containing 0.2% polyvinyl pyridine and The 4mol/L Lithium hydrate of 0.1% polyacrylamide and 6mol/L potassium hydroxide solution, prepare containing EDTA, shitosan and ammonia Compound complex agent solution, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution cocurrent simultaneously Pump in reactor, 40 DEG C of bath temperature, speed of agitator is 1200rpm, controls the molar average concentration of EDTA in reaction solution For 0.2mol/L；In reaction solution, the average quality concentration of shitosan is 19%；The molar average of ammonium ion in reaction solution Concentration is 3.5mol/L, and control ph is 13, and mean residence time is more than 30 hours, more than successive reaction 36h.Overflow is obtained To precipitate filter, washing, be dried after obtain lithium-rich manganese-based anode material precursor.Body before gained lithium-rich manganese-based anode material Body is in spherical, even particle size distribution, and D50 is 10 μm, and capacity is more than 248mAh/g, tap density 1.5g/cm3.
Embodiment 7
By NiSO4、Co(NO3)2、Mn(NO3)2In molar ratio Mn: Ni: Co=70: 15: 15 proportions nickel salt, cobalt salt, The mixed aqueous solution of manganese salt, nickel, cobalt, the hybrid ionic concentration of manganese are 2.5mol/L, prepare containing 0.2% polyethyleneimine and The 3mol/L potassium hydroxide of 0.3% polyacrylamide and 1mol/L sodium hydroxide solution, prepare containing EDTA, shitosan and ammonia Compound complex agent solution, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution cocurrent simultaneously Pump in reactor, 40 DEG C of bath temperature, speed of agitator is 1200rpm, controls the molar average concentration of EDTA in reaction solution For 0.1mol/L；In reaction solution, the average quality concentration of shitosan is 2%；In reaction solution, the molar average of ammonium ion is dense Spend for 0.5mol/L, and control ph is 10.5, mean residence time is more than 20 hours, more than successive reaction 24h.Overflow is obtained To precipitate filter, washing, be dried after obtain lithium-rich manganese-based anode material precursor.Body before gained lithium-rich manganese-based anode material Body is in spherical, even particle size distribution, and D50 is 10 μm, and capacity is more than 250mAh/g, tap density 1.7g/cm3.
Embodiment 8
By NiSO4、CoSO4、MnCl2Mn: Ni: Co=65: 15: 20 proportions nickel salt, cobalt salt, manganese salt in molar ratio Mixed aqueous solution, nickel, cobalt, the hybrid ionic concentration of manganese are 2.5mol/L, prepare poly- containing 0.2% polyethyleneimine and 0.3% The 3mol/L potassium hydroxide of acrylamide and 2mol/L sodium hydroxide solution, prepare compound containing EDTA, shitosan and ammonia Enveloping agent solution, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution, cocurrent pumps into simultaneously In reactor, 40 DEG C of bath temperature, speed of agitator is 1200rpm, and in control reaction solution, the molar average concentration of EDTA is 0.1mol/L；In reaction solution, the average quality concentration of shitosan is 4%；The molar average concentration of ammonium ion in reaction solution For 0.5mol/L, and control ph is 10.5, and mean residence time is more than 10 hours, more than successive reaction 24h.Overflow is obtained Precipitate filter, washing, be dried after obtain lithium-rich manganese-based anode material precursor.Gained lithium-rich manganese-based anode material precursor In spherical, even particle size distribution, D50 is 10 μm, and capacity is more than 240mAh/g, tap density 1.42g/cm3.
Embodiment 9
By NiCl2、CoSO4、MnCl2Mn: Ni: Co=55: 15: 30 proportions nickel salt, cobalt salt, manganese salt in molar ratio Mixed aqueous solution, nickel, cobalt, the hybrid ionic concentration of manganese are 2.5mol/L, prepare poly- containing 0.2% polyethyleneimine and 0.3% The 1mol/L potassium hydroxide of acrylamide and 2mol/L sodium hydroxide solution, prepare compound containing EDTA, shitosan and ammonia Enveloping agent solution, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution, cocurrent pumps into simultaneously In reactor, 40 DEG C of bath temperature, speed of agitator is 1200rpm, and in control reaction solution, the molar average concentration of EDTA is 0.1mol/L；In reaction solution, the average quality concentration of shitosan is 10%；In reaction solution, the molar average of ammonium ion is dense Spend for 0.5mol/L, and control ph is 10.5, mean residence time is more than 30 hours, more than successive reaction 48h.Overflow is obtained To precipitate filter, washing, be dried after obtain lithium-rich manganese-based anode material precursor.Body before gained lithium-rich manganese-based anode material Body is in spherical, even particle size distribution, and D50 is 10 μm, and capacity is more than 242mAh/g, tap density 1.55g/cm3.
Embodiment 10
By NiCl2、CoCl2、MnSO4Mn: Ni: Co=64: 18: 18 proportions nickel salt, cobalt salt, manganese salt in molar ratio Mixed aqueous solution, nickel, cobalt, the hybrid ionic concentration of manganese are 2.5mol/L, prepare poly- containing 0.2% polyethyleneimine and 0.3% The 3mol/L potassium hydroxide of acrylamide and 2mol/L sodium hydroxide solution, prepare compound containing EDTA, shitosan and ammonia Enveloping agent solution, then by nickel salt, cobalt salt, the mixed aqueous solution of manganese salt, aqueous slkali, compound complex agent solution, cocurrent pumps into simultaneously In reactor, 40 DEG C of bath temperature, speed of agitator is 1200rpm, and in control reaction solution, the molar average concentration of EDTA is 0.1mol/L；In reaction solution, the average quality concentration of shitosan is 2%；The molar average concentration of ammonium ion in reaction solution For 0.5mol/L, and control ph is 10.5, and mean residence time is more than 20 hours, more than successive reaction 24h.Overflow is obtained Precipitate filter, washing, be dried after obtain lithium-rich manganese-based anode material precursor.Gained lithium-rich manganese-based anode material precursor In spherical, even particle size distribution, D50 is 10 μm, and capacity is more than 250mAh/g, tap density 1.6g/cm3.

Claims (10)

1. a kind of preparation method of lithium-rich manganese-based anode material hydroxide precursor is it is characterised in that comprise the following steps：
(1) according to molecular formula Mn of hydroxide precursorxCoyNi1-x-y(OH)2The molar ratio nickel salt of middle Mn, Co, Ni, cobalt Salt, the mixed solution of manganese salt, wherein, 0.5 ＜ x ＜ 1,0 ＜ y ＜ 0.5, x+y ＜ 1；
(2) prepare the alkaline aqueous solution containing additive, described additive is polyvinyl pyridine, polyacrylamide, polyethyleneimine One or more of amine；Prepare containing EDTA, shitosan, ammonia compound complex agent solution；
(3) under inert gas shielding, by nickel salt, cobalt salt, the mixed solution of manganese salt, the alkaline aqueous solution containing additive, with And carry out successive reaction in the injection successive reaction kettle of the compound complex agent solution cocurrent containing EDTA, shitosan, ammonia, control anti- Answer the mean concentration of EDTA in solution, shitosan, ammonium ion, and control the pH value of reaction solution to be 9～13, when averagely stopping Between be more than 10 hours, reaction temperature be 30～80 DEG C, mixing speed be 100～2000rpm；
(4) reactor natural excrement feed liquid is filtered, washs, being dried to obtain lithium-rich manganese-based anode material hydroxide precursor.
2. lithium-rich manganese-based anode material hydroxide precursor according to claim 1 preparation method it is characterised in that Described nickel salt, manganese salt, cobalt salt are respectively one or more of sulfate, nitrate or chlorate.
3. the preparation method of lithium-rich manganese-based anode material hydroxide precursor according to claim 1 and 2, its feature exists In, nickel ion in described nickel salt, cobalt salt, the mixed solution of manganese salt, cobalt ion, the total mol concentration of manganese ion be 0.8～ 3.0mol/L.
4. lithium-rich manganese-based anode material hydroxide precursor according to claim 1 preparation method it is characterised in that Described alkaline aqueous solution is the mixed solution of one or more of NaOH, KOH and LiOH aqueous solution.
5. lithium-rich manganese-based anode material hydroxide precursor according to claim 4 preparation method it is characterised in that OH in described alkaline aqueous solution-Molar concentration be 1～12mol/L.
6. lithium-rich manganese-based anode material hydroxide precursor according to claim 1 preparation method it is characterised in that In described alkaline aqueous solution, the mass concentration of additive is 0.01%～0.3%.
7. lithium-rich manganese-based anode material hydroxide precursor according to claim 1 preparation method it is characterised in that In described reaction solution, the molar average concentration of EDTA controls in 0.0001～0.3mol/L.
8. lithium-rich manganese-based anode material hydroxide precursor according to claim 1 preparation method it is characterised in that In described reaction solution, the average quality concentration of shitosan controls 0.01%～20%.
9. lithium-rich manganese-based anode material hydroxide precursor according to claim 1 preparation method it is characterised in that In described reaction solution, the molar average concentration of ammonium ion controls in 0.01～4mol/L.
10. the preparation method of lithium-rich manganese-based anode material hydroxide precursor according to claim 1, its feature exists In described lithium-rich manganese-based anode material hydroxide precursor is spherical in shape or spherical, and D50 is 5～20 μm, and tap density is big In 1.3g/cm3.
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